IIIUSOO5728376A United States Patent 19 11 Patent Number: 5,728,376 Attygalle et al. 45) Date of Patent: Mar. 17, 1998

54. TETRADECATRIENYLAND Attygalle, et al. "Gas-Phase Infrared Spectroscopy for TETRADECADENYLACETATES AND Determination of Double Bond Configuation of Monoun THER USE ASSEX ATTRACTANTS FOR saturated Compounds." Analytical Chemistry, TOMATO PESTS 66(10): 1696-1703 (1994). Nesbitt. et al., "Identification of components of the female 75) Inventors: Athula B. Attygalle, Ithaca, N.Y.; sex pheromone of the potato tuber moth, Scrobipalipopsis Gulab N. Jham, Vigosa, Brazil; solanivora, ' Entomol. exp. appl. 38:81-85(1985). Alessvatoš, Prague, Czech Rep.; Rosa Persoons, et al. "Sex pheromone of the potato tuberworm T.S. Frighetto, Campinas, Brazil moth, Phthorimaea operculella: isolation, identification and field evaluation." Ent. exp. & appl. 20:289-300 (1976). 73) Assignee: Cornell Research Foundation, Inc., Renou, et al., "L'acétoxy-1 dodécéne 3E, composant prin Ithaca, N.Y. cipal de la phéromone sexuelle de la betterave: Scrobipalpa ocellatella Boyd. (Lépidoptere Gelechiidae).” Z. ang. Ent. (21) Appl. No.: 428,406 90:275-279 (1980). Roelofs, et al. "Lepidopterous sex attractants discovered by 22 Filed: Apr. 25, 1995 field screening tests”. J. Econ. Entomol. 63(5):969-974 (51) Int. Cl' ...... A01N 31/02; CO7C 33/02: (1970). CO7C 33/048; CO7C 21/02 Svatos, et al., "Synthesis of deuterium labeled polyunsatu (52) U.S. Cl...... 424/84; 560/261; 568/849; rated fatty acids." Tetrahedron Letters. 35(51):9497–9500 568/850; 568/873; 568/903; 43/132.1 (1994). 58 Field of Search ...... 424/405, 84; 560/261; Primary Examiner-Edward J. Webman 568/849, 850, 873,903 Attorney, Agent, or Firm-Nixon, Hargrave, Devans & Doyle 56 References Cited ABSTRACT U.S. PATENT DOCUMENTS 57 3,980,771 9/1976 Meijer et al...... 424/84 The present invention is directed to compounds useful as 3,991,125 11/1976 Labovitz et al. ... 424/84 moth attractants and to methods for controlling populations 4,147,771 4/1979 Struble et al...... 424/84 of the tomato moth Scrobipalpuloides absoluta with these 4,189.614 2/1980 Samain ...... 568/908 compounds. The compounds are 3,8,11-tetradecatrienyl 4,284,622 8/1981 Underhill et al...... 424/84 acetates, 3.8-tetradecadienyl acetates, 3, 11-tetradecadienyl 4,296,042 10/1981 Muchowski et al. 260/345.9 R acetates, and 8.11-tetradecadienyl acetates. Preferred com 4,609.498 9/1986 Banasiak et al. 260/410.9 R pounds are (3E,8Z.11Z)-3,8,11-tetradecatrienyl acetate, (3E, 4,654,461 3/1987 Drake et al. . ... 585/600 8Z)-3,8-tetradecadienyl acetate, (3E, 11Z)-3, 11- tetradecadi 4,834,745 5/1989 Ogawa et al...... 424/409 enyl acetate, and (82.11Z)-8-11-tetradecadienyl acetate. The 4,844,916 7/1989 Ogawa et al...... 424/409 compounds can be used as an attractant in moth traps

5,236,715 8/1993 McDonough et al...... 424/84 5,252,326 10/1993 Novotny et al...... 424/54 comprising, in addition to the compounds, a moth restraint. 5,380,524 1/1995 McDonough et al...... 424/84 Alternatively, the compounds of the present invention can be combined with a biocontrol agent or an insecticide for use as OTHER PUBLICATIONS a moth control composition. Synthesis of (3E.8Z.11Z)-3.8. Attygalle, "Gas phase infrared spectroscopy in characteriza 11-tetradecatrienyl acetate is described. tion of unsaturated natural products.” Pure & Appl. Chem. 66(10/11):2323-2326 (1994). 62 Claims, 5 Drawing Sheets

OO/ PEAK 2

PEAK --- 22:O2 23:22 24.2 26:02 27:22 U.S. Patent Mar 17, 1998 Sheet 1 of 5 5,728,376

o CN

- U O O na n N N Na O CO

O VO N 92 w N O s

N 2 d ) s in S n S. N n O 9

C O N n r N O VO

O ar S On 9 N 3SNOS3& 30 NWONSW U.S. Patent Mar. 17, 1998 Sheet 2 of 5 5,728,376

woul...... as a cowr-erarwira-Re

Frymaverseasureseries assovernow co-open-wxor O a is s sa o 4. s a 4 is a

g

8

ww.exex mayorr 8 g S g

9 g

O O. O. O O. O. O. O O. O. S On Oo N to ur N r ra. ONONOSB& S3WWO 99W. N3O3 U.S. Patent Mar. 17, 1998 Sheet 3 of 5 5,728,376

4-1-12N \SN 30cm &z/ I v--A \ \S2.

H |N INNINr. CONTROL 1 g 10 ug 100g FEMALE F.G. 6 U.S. Patent Mar. 17, 1998 Sheet 5 of 5 5,728,376

HNHHNTH | | | |N| || | | |N|NNN 3-LAM L.-5AM 5-6AM 6-7AM 7-8AM 8-9AM FIG.7 5,728,376 1 2 TETRADECATRENYLAND In recent years, compounds known as pheromones have been recognized as useful components of successful pest TETRADECADENYLACETATES AND control programs. A pheromone is generally defined as a THEIR USE ASSEXATTRACTANTS FOR chemical substance secreted by living organisms, including TOMATO PESTS insects, to convey information or produce a specific response in other individuals of the same species. Sex This invention was made through the support of the pheromones may be a single compound but typically take National Science Foundation (Grant INT9202380). The the form of a complex, volatile blend of compounds which Federal Government may retain certain rights in the inven is, for example, secreted during the mating cycle. As such, tion. sex pheromones often serve as "attractants"; that is, the FIELD OF THE INVENTION pheromone attracts insects of the same species to the loca This invention relates to moth attractants and to methods tion of the pheromone emission. Attractants for many species of moth have been identified. for synthesizing and using these attractants. For example, Persoons et al. "Sex pheromone of the potato BACKGROUND OF THE INVENTION 15 tuberworm moth, Phthorinaea operculella: isolation, iden Tomato (Lycopersicon esculentum) is an economically tification and field evaluation." Entomol. Exp. Appl. important plant which is cultivated extensively all over the 20:289-300 (1976), disclose the use of (4E,7Z.10Z)-4,7,10 world. However, tomato is extremely susceptible to insect tridecatrienylacetate, together with the corresponding diene, attack by Scrobipalpuloides absoluta (Lepidoptera: (4E.7Z)-4,7-tridecatrienyl acetate, as a sex attractant for Gelechiide) (Gallo et al. in Manual de Entomologica 20 Phthorimaea operculella. Nesbitt et al., "Identification of Agricola, 2nd ed., Ceres, ed., Sao Paulo, Brazil, 649 (1988)). components of the female sex pheromone of the potato tuber In the past, the pest has been known as Scrobipalpa absoluta moth, Scrobipalipopsis solanivora,' Entomol. Exp. Appl., and Scrobipalpulpa absoluta (Meyrick). It is known locally 38:81-85 (1985), have identified (E)-3-decen-1-yl acetate as as "traga-do-tomateiro” in Brazil and as "polilla del tomate" a pheromone constituent of the potato tuber moth. Scrobi in other Latin American countries. The pest is particularly 25 palposis solanivera Povolny. Pheromones for some insects active in Latin America where it causes severe damage in all from the Scrobipalpa family have also been identified. These tomato growing countries including Venezuela, Columbia, include: (E)-3-tridecen-1-yl acetate for the tobacco stem Chile, Ecuador, Bolivia, Peru and Uruguay. Brazil, which borer moth, Scrobipalpa heliopa (Lower) (Baker et al. "Sex has about 55,000 acres under tomato cultivation, has been pheromone of tobacco stem borer Scrobipalpa heliopa particularly affected. Since 1981, when Moreira et al., (Lower) (Lepidoptera: Gelechiidae)." J. Chem Ecol., "Ocorrencia de Scrobipalpula absoluta danificando 11:989–998 (1985)) and (E)-3-dodecen-1-yl acetate for the tomateiro rasteiro em Jaboticabal," S.D. in Congresso sugar beet moth, Scrobipalpa ocellatella Boyd (Renou et al. Brasileiro de Entomologic Fortaleza Ce, 58 (1981), first "L'acétoxy-1 dodécene 3E, composant principal de la reported the pest in Brazil in the state of Sao Paulo. phéromone sexuelle de lateigne de la betterave: Scrobipalpa infestation has spread to other states, such as Minas Gerais, 35 ocellatella Boyd. (Lépidoptère Gelechiidae)," Z. ang. Salvador, Espirito Santo and Rio de Janeiro. Losses of up to Entomol, 90:275-289 (1980)). 100% have been described. No attractant has yet been identified for the tomato moth, The need to suppress Scrobipalpuloides absoluta popu Scrobipalpuloides absoluta, and, therefore, blanket spraying lations ("S. absoluta") has resulted in the application of large of broad-based insecticides, with all its associated limita amounts of conventional, broad-based insecticides by blan tions and adverse impacts, remains the dominant control ket spraying. The method, however, has serious limitations. method. For these and other reasons, a need exists for It is now well established that continuous or repeated pheromone attractants for S. absoluta and methods of pesticide use results in the emergence of insect strains which employing this attractant to control S. absoluta populations. resist the chemicals being applied, making subsequent insect SUMMARY OF INVENTION control more difficult. Furthermore, application of broad 45 based pesticides upsets delicate natural balances by elimi The present invention relates to attractants for moths as nating non-targeted species, including natural predators of well as to the synthesis and use of these compounds. One the pest and pollinators. The use of insecticides also aspect of the present invention relates to an isolated 3,8,11 adversely impacts the farmers, both economically and medi tetradecatrienyl acetate. cally. The cost of broad-based insecticides and the cost of 50 Another aspect of the present invention relates to an their application place a heavy financial burden on poor isolated tetradecadienyl acetate. The tetradecadienyl acetate farmers. The use of pesticides also subjects farmers and is selected from the group consisting of a 3.8- other inhabitants living near tomato fields to the hazards of tetradecadienyl acetate, a 3.11-tetradecadienyl acetate, and exposure. This exposure is particularly severe in Latin an 8,11-tetradecadienyl acetate. America, where farmers' residences are typically in close 55 The present invention also provides an attractant blend proximity to their tomato fields. Moreover, it is generally comprising two or more compounds. The compounds are known that some pesticide residues enter and move along selected from the group consisting of a 3,8-tetradecadienyl the food web, thus exposing virtually all living organisms to acetate, a 3.11-tetradecadienyl acetate, an 8, 11 these hazardous chemicals. The drawbacks associated with tetradecadienyl acetate, and a 3.8.11-tetradecatrienyl blanket spraying are exacerbated by the fact that such acetate. spraying must be repeated at regular intervals, typically The present invention further provides a moth trap com weekly, during the growing season because the insecticide is prising a restraining member and a moth attractant used in effective only against adult moths. Moths in the larval stage. conjunction with the moth restraining member. The moth having burrowed inside the leaves, stems, and fruits, remain attractant is selected from the group consisting of a 3.8- unexposed and unaffected. Accordingly, there is a continu 65 tetradecadienyl acetate, a 3.11-tetradecadienyl acetate, an ing need for the development of safe, effective, and envi 8, 11-tetradecadienyl acetate, a 3.8, 11-tetradecatrienyl ronmentally compatible moth control techniques. acetate, and mixtures thereof. 5,728,376 3 The invention further provides a moth control composi tion comprising a moth attractant and either an insecticide or a biocontrol agent. In each of these moth control VVVVx compositions, the moth attractant is selected from the group consisting of a 3.8-tetradecadienyl acetate, a 3.11 5 tetradecadienyl acetate, an 8.11-tetradecadienyl acetate, a wherein X is a halogen. 3.8, 11-tetradecatrienyl acetate, and mixtures thereof. The tetradecadienyl and tetradecatrienyl acetates of the A method for attracting moths to a particular location is present invention are effective and useful moth attractants. also provided in accordance with the present invention. They are particularly well suited for attracting moths of the Moths are attracted by providing at the particular location Scrobipalpuloides absoluta species. These attractants and about 10 picograms to about 10 milligrams of a moth the methods of using them provide a biorational alternative attractant. The moth attractant is selected from the group to blanket application of broad-based pesticides for combat consisting of a 3.8-tetradecadienyl acetate, a 3,11 ting S. absoluta infestation. Reducing pesticide use benefits tetradecadienyl acetate, an 8.11-tetradecadienyl acetate, a the environment, contributes to the conservation of biodi 3.8.11-tetradecatrienyl acetate, and mixtures thereof. versity of species, and decreases indiscriminate elimination The present invention further provides a method for 15 of non-targeted predators of the moth and pollinators. controlling a population of moths. According to this method Moreover, reduced dependence on costly pesticides pro of the subject invention, moths are attracted to a particular vides a direct economic benefit to farmers plagued by S. location with about 10 picograms to about 10 milligrams of absoluta. a moth attractant selected from the group consisting of a 3,8-tetradecadienyl acetate, a 3.11-tetradecadienyl acetate, BRIEF DESCRIPTION OF THE DRAWINGS an 8,11-tetradecadienyl acetate, a 3.8.11-tetradecatrienyl FIG. 1 is a section of the reconstructed gas chromatogram acetate, and mixtures thereof. Proximate to this particular obtained from the volatiles present in a female pheromone location, the moths are exposed to an agent which impairs gland extract of S. absoluta (30 mx0.22 mm fused-silica the moths' ability to mate. Suitable agents include, for capillary column coated with FFAP stationary phase; tem example, a restraining device, an insecticide, or a biocontrol 25 perature program: 40° C. for 4 min, 6°C/min to 190° C.). agent. FIG. 2 is an electron-ionization mass spectrum (70 eV) of The present invention also provides a method of disrupt the major female sex pheromone component of S. absoluta. ing mating of moths in a particular area. The method FIG. 3 is a bar graph depicting the percentage of male includes providing in the particular area a quantity of an 30 moths responding in a wind-tunnel behavioral bioassay. attractant selected from the group consisting of a 3.8- Stippled, open, and black bars represent wing fanning, tetradecadienyl acetate, a 3.11-tetradecadienyl acetate, an oriented flight, and landing-at-the-source behavior, respec 8, 11-tetradecadienyl acetate, a 3.8.11-tetradecatrienyl tively. Behavior of 30 males were observed for each test acetate, and mixtures thereof. The quantity provided is stimulus. Hexane (100 l) and different amounts (10 ng-10 above that emanating from moths and sufficient to prevent 35 ug) of (3E, 87.11Z)-3.8-11-tetradecatrienyl acetate applied pheromone communication. to rubber septa, and nine calling females were used as The invention also relates to a method of synthesizing stimuli. (3E,82,11Z)-3,8,11-tetradecatrienyl acetate. The method FIG. 4A-4E are drawings of different types of traps. involves providing trienyl alcohol having the formula: FIG. 5 is a histogram depicting the average number of males caught per night per trap (N=15) for each of trap (II) designs A-E. Each trap was baited with 1 ug of synthetic VVVVVVol. (3E,8Z.11Z)-3,8-11-tetradecatrienyl acetate on a rubber dis and acetylating the alcohol. penser. Vertical bars represent standard deviations. Another aspect of the present invention pertains to a series FIG. 6 is a histogram depicting the average number of of compounds from which (3E,8Z.11Z)-3.8.11 45 male moths caught per trap (N=20) per night by traps baited tetradecatrienyl acetate can be prepared. One such com with 1, 10, or 100 g of synthetic (3E.8Z.11Z)-3.8-11 pound is a trienyl alcohol having the formula: tetradecatrienyl acetate on a rubber dispenser, or one one day-old virgin female. Control baits were treated with 100 ul II of distilled hexane. Vertical bars represent standard devia VVVVVVoit 50 tions. FIG. 7 is a histogram showing the average number of Another such compound is a dieneynyl alcohol having the males caught per trap (N=8) per hour by traps baited with 1 formula: pug of synthetic (3E.8Z.11Z)-3,8-11-tetradecatrienyl acetate OH on a rubber dispenser. Vertical bars represent Standard 55 Deviations. DETALED DESCRIPTION OF THE INVENTION The invention also pertains to a protected dieneynyl alcohol The present invention relates to compounds useful as having the formula: attractants for moths, the synthesis of these compounds, and the use of these compounds in the management of these OY pests. One aspect of the present invention relates to an isolated 3,8,11-tetradecatrienyl acetate, having the following 65 general formula: wherein Y is an alcohol protecting group, and a dienylhalide CHCH-CH=CHCH-CH=CHCHCHCH-CH=CHCHCHOC(O) having the formula: CH, 5,728,376 5 6 include acid catalyzed reaction with acetic acid, reaction As used herein, an isolated compound is one which is with acetyl chloride. acid catalyzed transesterification with, substantially free of the tissue in which it naturally occurs. for example, an alkyl acetate, and reaction of the alcohol It is to be understood that the isolated compounds of the with acetic anhydride. Preferably, acetylation is effected present invention are not limited to any particular method of with acetic anhydride in a basic solvent, preferably pyridine. preparation and include, for example, compounds which are 5 The trienyl alcohol of Formula (II), used in the above prepared by extraction from natural sources as well as those preparation of the acetate of Formula (I), can be prepared by prepared by chemical synthesis. Preferably, the 3.8.11 a variety of conventional synthetic routes. Examples of tetradecatrienyl acetate is substantially pure. In this context, general synthetic strategies of isomerically pure polyeneyl substantially pure means substantially free of compounds alcohols are provided in Bestmann et al., other than the particular 3.8.11-tetradecatrienyl acetate. 10 "Insektenpheromone, Teil 1, Chemische Struktur and Each of the three double bonds in this compound may Synthese, Seifen-die-Fette-Wachse 114:612-621 (1988) independently assume either the trans ("E") or cis ("Z") and Baker et al. "Insect pheromones and related natural form. The 3.8.11-tetradecatrienyl acetate can be (3E.8E, products," Natural Product Reports 1:299-318 (1984), 11E)-3,8,11-tetradecatrienyl acetate, 3E,8E.11Z)-3.8, 11 which are hereby incorporated by reference. Preferably, the tetradecatrienyl acetate, 3E,8Z.11E)-3.8.11-tetradecatrienyl 15 trienyl alcohol is prepared by reduction of the corresponding acetate, 3Z.8E.11E)-3,8,11-tetradecatrienyl acetate, 3E.8Z. diemeynyl alcohol, having the formula: 11Z)-3,8,11-tetradecatrienyl acetate, (3Z.8E.11Z)-3,8,11 tetradecatrienyl acetate, (3Z.8Z.11E)-3,8,11-tetradecatrienyl OH III) acetate, or (3Z,8Z.11Z)-3,8,11-tetradecatrienyl acetate. W Preferably, the 3,8.11-tetradecatrienyl acetate is (3E,8Z.11Z) -38, 11-tetradecatrienyl acetate, having the formula Choice of reducing agent and reaction conditions are governed by the desirability of preferentially producing the I trans isomer and the desirability of minimizing reduction of VVVVVVococh the resulting double bond or either of the two other double Another aspect of the present invention relates to an 25 bonds. Suitable reducing reagents include alkali metal in isolated tetradecadienyl acetate. The tetradecadienyl acetate liquid ammonia. The alcohol of Formula (III) is preferably is selected from the group consisting of 3,8-tetradecadienyl reduced with lithium tetrahydridoaluminate in a dry aprotic acetates, 3.11-tetradecadienyl acetates, and 8, 11 solvent such as diglyme, at elevated temperatures, as tetradecadienyl acetates. Suitable tetradecadienyl acetates described by Rosiet al., "Stereoselective reduction of B- and include (3E,8E)-3,8 tetradecadienyl acetate, (3E.8Z)-3,8- co-alkynols to the corresponding (E)-alkenols by lithium tetradecadienyl acetate, (3Z8E)-3,8-tetradecadienyl acetate. tetrahydridoaluminate.” Synthesis 1977:561-562, which is (3Z,8Z)-3,8-tetradecadienyl acetate, (3E, 11E)-3.11. hereby incorporated by reference. Preferably, the reduction tetradecadienyl acetate, (3E.11Z)-3, 11-tetradecadienyl is conducted at 120-140° C. for 2-5 hours. Heating at acetate. (3Z.11E)-3.11-tetradecadienyl acetate, (3Z,112)-3, higher temperatures or for longer times or both results in 11-tetradecadienyl acetate, (8E.11E)-8, 11-tetradecadienyl 35 product contaminated with over-reduced and isomerizated acetate, (8E.11Z)-8.11-tetradecadienyl acetate. (87.11E)-8, polyenols and, consequently, is preferably avoided. 11-tetradecadienyl acetate, and (3E, 112)-8, 11 The dienynol of Formula (III) can be prepared by a variety tetradecadienyl acetate. Preferred tetradecadienyl acetates of synthetic pathways. In a preferred synthetic scheme, a are (3E,82)-3,8-tetradecadienyl acetate. (82.11Z)-8, 11 dienyl halide having the formula: tetradecadienyl acetate, and (3E, 11 Z)-3, 11 tetradecadedienyl acetate. Respectively, these compounds (IV) have the following formulas: VVVVx wherein X is a halogen atom, is alkylated with an alkali 45 metal salt of a protected 3-butynol having the formula: V

wherein M is an alkali metal and Y is an alcohol protecting group, thus producing a protected dienynyl alcohol having VTVVVVVococ, the formula: OY VI preferably, the tetradecadienyl acetate is substantially pore. y In this context, substantially pure means substantially free of 55 compounds other than the particular tetradecadienyl acetate. wherein Y is the same alcohol protecting group used to (3E.8Z.11Z)-3.8.11-tetradecatrienyl acetate can be syn protect the butynol of Formula (V). X, the halogen atom in thesized by providing the trienyl alcohol having the formula: Formula (IV), can be chlorine, bromine or iodine, preferably bromine. The alkali metal which forms the salt of the II) protected 3-butynol, M in Formula (V), can be sodium, VVVVVVof potassium, or, preferably, lithium. The protected 3-butynol and acetylating the alcohol. Acetylation can be effected by alkali metal salt can be prepared by treating the correspond any of the established techniques, such as, for example, ing 3-butynol with an alkyl alkali metal compound, such as, those reviewed in Kemp et al., Organic Chemistry, Worth 65 for example, n-butyllithium, in cold, dry aprotic solvent, Publishers. New York, 370-378 (1980), which is hereby such as, for example, tetrahydrofuran, diglyme, glyme, ethyl incorporated by reference. Suitable acetylation methods ether, or an alkane solvent. The 3-butynol alkali metal salt 5,728,376 7 8 can be reacted, without further purification, with the dienyl Alternatively, 1-(tetrahydropyran-2-yloxy)-4,7-decadiene, halide dissolved in a dry, aprotic solvent, preferably having and analogs thereof, can be prepared using the coupling Lewis base activity, such as, for example, hexamethylphos method described in Lapitskaya et al., "A chemoselective phorous triamide (“HMPT"), or, preferably, 1,3-dimethyl-3, synthesis of functionalized 1,4-alkadiynes (skipped 4.5,6-tetrahydro-2(1H)-pyrimidine. The reaction is carried diacetylenes). Synthesis, 1993:65-66, which is hereby incor out for a time period from 0.1 to 2.0 hours, preferably 0.5 porated by reference. Because of its instability, the diyne is hours, at a temperature of -10° to 5°C., preferably 0°C. The preferably used immediately and without further purifica reaction is advantageously heated or cooled, depending on tion. the reactivity of the alkali metal employed. Where the The diyne is then hydroborated, such as by reaction with lithium salt of the 3-butynol is used, the especially exother an alkylborane, preferably a dicyclohexylborane, the prepa mic reaction can be controlled with a cooling bath. The 10 ration and use of which are detailed in Brown et al., protected dienynol is then deprotected, thereby providing "Hydroboration 45. New, convenient preparation of repre the dienynol of Formula (III). Y, the alcohol protecting sentative borane reagents utilizing borane-methylsulphide." group in Formula (V) and Formula (VI), can be any group J. Org. Chem, 42:1392-72 (1977), which is hereby incor which inhibits displacement of the hydroxyl in a nucleo porated by reference. The reaction is carried out in an aprotic philic attack. Preferably. Y is tetrahydropyranyl. Other suit 15 solvent, such as benzene, toluene, xylenes, or, preferably, able alcohol protecting groups are described in Kocienski, tetrahydrofuran, for a period of 5 to 15 hours, preferably 12 Protecting Groups, Stuttgart: Thieme Publishers, 1994, hours, at a temperature of 10° to 50° C., preferably 30° C. which is hereby incorporated by reference, such as, for The hydroboration product, a vinyl borane, is then hydro example, benzyl, benzhydryl, trityl, and trimethylsilyl. The lyzed to the vinyl borate by stirring for 5 to 10 hours, method of deprotection depends on the nature of the pro preferably 7 hours, at -10° to 10° C., preferably 0°C., with tecting agent. Where the protecting agent is benzyl, depro a weak acid, preferably acetic acid. After basifying the tection may be effected by acid treatment or by mild reaction mixture, with, for example, sodium hydroxide, the hydrogenation. Where the preferred tetrahydropyranyl pro vinyl borate is then carefully oxidized, preferably with tecting group is employed, deprotection can be effected with hydrogen peroxide, at 10° to 50° C., preferably 30° C., for an acid in a polar solvent, preferably with inactivated ion 25 a time period of 0.05 to 2 hours, preferably 1 hour, to form exchanger, such as DOWEXTM (Dow Chemical, Midland, a mixture of the protected and deprotected dienyl alcohol. Mich.), in methanol. The mixture is then converted into dienyl halide by Various synthetic schemes can be employed to provide a reaction of the mixture with a suitable halogenating reagent. dienyl halide of Formula (IV) in the aforedescribed pre Such suitable reagents include bromine and mixtures of ferred preparation of the Formula (VI) dienynol. In a pre 30 tetrabromomethane and triphenyl phosphine. as described in ferred method, a protected 4-pentyn-1-ol, having the for Wagner et al., "Direct conversion of tetrahydropyranylated mula: alcohols to the corresponding bromides.” Tetrahedron Lett, 30:557-558 (1989) and Sonnett, "Direct conversion of an H.-E. (VII) alcohol tetrahydropyranyl ether to a bromide, chloride, 35 methyl ether, nitrile, or trifluoroacetate, Synthetic V oz Communications, 6:21-26 (1976), which are hereby incor wherein Z is an alcohol protecting group, is converted into porated by reference. Alternatively, and preferably, conver a Grignard reagent, and then reacted with pentynyl tosylate sion to the halide is effected by treating the mixture of dienyl to form a diyne having the formula: alcohol and protected dienyl alcohol with triphenyl phos phine dibromide such as described by Bestmann et al., VIII) "Pheromones:87. An efficient synthesis of (6E, 11Z)-6.11 hexadecadienyl acetate and (6E.11Z)-6,11-hexadecadienal: Female sex pheromone of Antheraea pernyi and A. polyphe wherein Z is the same alcohol protecting group used to mus (Lepidoptera: Saturniidae).” Synthesis, protect the pentynol of Formula (VTI). The reaction is 45 1992:1239-1241, which is hereby incorporated by refer carried out in a dry, aprotic solvent, such as tetrahydrofuran, ence. Briefly, the triphenylphosphine dibromide is formed glyme, diglyme or ethyl ether, with tetrahydrofuran being by treating triphenylphosphine with Brin a suitable solvent preferred. The reaction is effected by slowly mixing the at -10° to 10° C. preferably 0° C. for 0.1 to 0.5 hours, reactants, preferably by dropwise addition of the tosylate to preferably 0.35 hours. Suitable solvents include the Grignard reagent. at a temperature of -5° to 10° C. 50 dichloromethane, chloroform, tetrachloroethane, and, preferably 0° C. followed by stirring the mixture for a preferably, dichloromethane. The reaction of triphenyl phos period of 6 to 15 hours. preferably 12 hours. at 10° to 50° phine dibromide with dienyl alcohol mixture is carried out C.. preferably 30° C. The Grignard reaction can be at 10° to 50° C. preferably at room temperature, for 0.5 to catalyzed, for example. by cuprous iodide, as described by 2 hours, preferably 1 hour. Millar et al., "Short synthesis of 1.3Z.6Z.97-tetraene hydro 55 The present invention further relates to compounds carbons. Lepidopteran sex attractants," Can. J. Chem. described by Formula (II); Formula (III); Formula (IV), 64:2427-2430 (1986), which is hereby incorporated by wherein X is a halogen atom, preferably chlorine, bromine reference, or, preferably, by a cuprous bromide-methyl sul or iodine, most preferably, bromine; and Formula (VI). fide complex. Suitable alcohol protecting groups include wherein Y is an alcohol protecting group, preferably a benzyl, benzhydryl, trityl, and tetrahydropyranyl and are benzyl, benzhydryl. trityl, trimethylsilyl, or reviewed in Kocienski. Protecting Groups, Stuttgart: Thi tetrahydropyranyl, most preferably tetrahydropyranyl. eme Publishers (1994), which is hereby incorporated by These compounds, when treated in accordance with the reference. Preferably, Z is tetrahydropyranyl, and the pro procedures described hereinabove, form substances which tected 4-pentyn-1-ol is 1-(tetrahydropyran-2-yloxy)-4- attract moths. pentyne. Where the preferred protecting group is employed, 65 The present invention further relates to an attractant blend the diyne formed is 1-(tetrahydropyran-2-yloxy)-4,7- comprising two or more compounds. The compounds are decadiene (Formula (VIII), Z=tetrahydropyranyl). selected from the group consisting of a 3.8-tetradecadienyl 5,728,376 9 10 acetate, a 3, 11-tetradecadienyl acetate, an 8.11 and copolymers of ethylene and vinyl acetate containing tetradecadienyl acetate, and a 3.8.11-tetradecatrienyl 20% by weight or less of vinyl acetate are particularly acetate. Preferably, the 3,8-tetradecadienyl acetate is (3E, preferred. 8Z)-3,8-tetradecadienyl acetate, the 3.11-tetradecadienyl The shape and size of the dispenser are not critical. acetate is (3E,11Z)-tetradecadienyl acetate, and the 8.11 Suitable dispenser shapes include, for example, cylindrical, tetradecadienyl acetate is (87.11Z)-8, 11-tetradecadienyl such as a capillary tube, sealed at both ends, spherical, acetate. It is also preferred that at least one of the compounds ellipsoidal, or platelike. Preferably, the ratio of the outer in the attractant blend be a 3.8.11-tetradecatrienyl acetate, surface area of the dispenser to the amount of attractant most preferably (3E.8Z.11Z)-3,8.11-tetradecatrienyl acetate. contained therein is optimized using the guiding principles The compounds of the present invention are useful as 10 discussed in U.S. Pat. No. 4,834.745 to Ogawa et al... which attractants for moths, especially the moth Scrobipalpuloides is hereby incorporated by reference. For instance, when the absoluta. They may be used for attracting moths for pur outer surface area of the dispenser is great relative to the poses of studying the moths, for controlling the region they amount of attractant contained therein, the rate of attractant habitate, for controlling their ability to reproduce, and for emission can be undesirably large with a large difference controlling their lifespan. In addition, the compounds can be 15 between the initial and latest stages of serviceable life of the used for monitoring moth populations. dispenser so that the serviceable life would be unduly The present invention also relates to a moth trap which decreased. On the other hand, when the ratio is too small, the comprises a moth restraining member and a moth attractant rate of attractant emission can be undesirably low, so that the used in conjunction with the restraining member. The preferred concentration of the attractant is not maintained in restraining member can physically restrain, chemically the atmosphere. restrain, or entrap the attracted moths. The restraining mem Attractants, used in conjunction with the aforementioned ber can be an adhesive material, such as, for example, glue dispensers, are released over a sustained period of time, or tanglefoot. The restraining member can also be a which enhances their susceptibility to oxidative and photo mechanical barrier, such as a door constructed to allow chemical decomposition during the serviceable life of the moths to enter the trap but not exit. The restraining member 25 dispenser. When the attractant is susceptible to photochemi can also be an electrical device which shocks the moth cal decomposition, photochemical decomposition can be which has been attracted to the attractant, thereby rendering decreased by forming the barrier wall of a polymeric mate the moth incapable of escaping the trap. The trap may further rial admixed with an ultraviolet absorber, dye, or pigment or comprise an insecticide, whose action is enhanced by the by admixing the attractant with an ultraviolet absorber or an inability of the moth to readily escape from the restraint. The 30 antioxidant. Suitable antioxidants include 2,6-di-tert-butyl amount of insecticide used can be lethal for an exposed p-cresol (“BHT”). insect or at least sublethal but sufficient to incapacitate the Further details regarding the attractant dispensers and moth in regard to escape. The trap can further comprise one their use are disclosed in, for example, U.S. Pat No. or more supports on which one or more of the attractant, 4,834,745 to Ogawa et al. and U.S. Pat. No. 4,600,146 to adhesive and insecticide can be placed. The support can be 35 Ohno, which are hereby incorporated by reference. formed from any material suitable for supporting one or The traps can be of any suitable shape. Preferably, they more of the attractant, adhesive and insecticide, such as, for are cylindrical shaped with conical screen funnel entrances example, cotton, rubber, plastic, canvas, wood, or cardboard. at each end. The trap can be placed in trees or shrubs or Additionally or alternatively, the moth trap of the present suspended from or attached to poles mounted in the ground. invention can further comprise a dispenser which sus Preferably, the trap is placed from about 1 to about 2 meters, tainedly releases the moth attractant contained therein into more preferably about 1.2 meters, above the ground with the atmosphere, preferably at a constant rate over a length of one opening facing the prevailing wind. The amount of time. One suitable dispenser is described in U.S. Pat. No. attractant per trap can range from about 10 picograms to 4,834,745 to Ogawa et al., which is hereby incorporated by about 10 milligrams, preferably from about 1 nanogram to reference. It comprises a barrier wall made of a polymeric 45 1 microgram. material which is swellable with the attractant. The moth Further details regarding the use and construction of moth attractant, contained in an a hollow space defined by the traps are disclosed in U.S. Pat. No. 4,147,771 to Struble et barrier wall, permeates through the barrier wall and is al., U.S. Pat. No. 5.236,715 to McDonough et al., U.S. Pat. released from the outer surface thereof in the form of a No. 3.991,125 to Labovitz et al., U.S. Pat. No. 3,803.303 to vapor. 50 McKibben et al., and U.S. Pat. No. 3,980.771 to Meijer et The serviceable life of the dispenser depends on the al., which are hereby incorporated by reference. selection of the polymeric material forming the barrier wall The present invention further provides a moth control to match the respective attractant and the dimensions of the composition comprising an insecticide and a moth attractant. dispenser. Specifically, the equilibrium swelling of the poly Because many insecticides repel moths, the combination of meric material with the moth attractant should preferably be 55 an attractant and insecticide can have enhanced effectiveness in the range from about 2 to about 6% by weight at 20° C. over use of an insecticide alone. The insecticide?attractant When the equilibrium swelling is smaller than 2% by moth control composition can be in the form of, for example, weight, the rate of attractant emission is undesirably low, sprays, such as emulsifiable concentrates or wettable while, conversely, an equilibrium swelling larger that 6% by powders, aerosols, dusts, baits, granular formulations, and weight would result in an undesirably large rate of attractant laminated slow release formulations. The attractants, com emission. bined with the insecticide and used without a support, can be The equilibrium swelling of a polymeric material is a spread over the area of moth infestation, preferably as a mist parameter determined by the kind of the polymeric material. or a dust in a suitable carrier, such as vegetable oils, refined Polymeric materials suitable for use in the invention include mineral oils, rubbers, plastics, silica, diatomaceous earth, polyethylene, polypropylene, copolymers of ethylene and 65 and cellulose powder. Alternatively, the attractant can be vinyl acetate, polyvinyl chloride, cellulose acetate, formal combined with an insecticide in an amount sufficient to ized polyvinyl alcohol and the like, of which polyethylene fatally injure but not restrain the moth on a support without 5,728,376 11 12 a restraint. Suitable supports include those suitable for use in compositions are analogous to those used for exposing moth traps, examples of which are listed above. Insecticided moths with the biocontrol agent/attractant compositions. attractant moth control compositions on supports are Further details regarding the preparation and use of com advantageous, because they eliminate the need to spread bination of biocontrol agent/attractant and chemosterilant? insecticides unnecessarily. Alternatively, the insecticided attractant moth control compositions are disclosed, for attractant moth control composition can be used in traps example, in U.S. Pat. No. 5.236,715 to McDonough et al., (that is, in conjunction with a moth restraining member), as which is hereby incorporated by reference. described above. The moth attractants of the present invention can also be Further details regarding the combination of attractants used to disrupt mating of moths within a particular area. This and insecticides in moth control compositions in sprays, on O method includes providing in the particular area a quantity supports or in traps are disclosed in, for example, U.S. Pat. of an attractant above that emanating from moths, preferably No. 5,236.715 to McDonough et al., which is hereby incor a quantity sufficient to prevent pheromone communication. porated by reference. In this manner, potential mates are prevented from finding Suitable insecticides for use in the aforementioned moth each other, thus disrupting the ability of the moths to mate. traps and moth control compositions include, for example, 15 The moth attractant can be provided to the particular area by organophosphates, such as diazinon, chlorpyrifos, pro dispersing, such as by spraying or depositing, the attractant petamphos or acephate, carbamates, such as propoxur. over or in the particular area. Suitable carriers, such as pyrethroids, such as cypermethrin, sulfuramids, insect vegetable oils, refined mineral oils, rubbers, plastics, silica, growth regulators, or mixtures thereof. S.S'-(2- diatomaceous earth, and cellulose powder, can be advanta dimethylaminotrimethylene) bis(thiocarbamate) ("Cartap"). geously employed to aid in dispersing the attractant. ethyl 2-dimethoxythiophosphorylthio-2-phenylacetate Alternatively, the attractant can be provided by evaporating ("Phenthoate"), available commercially under the name the attractant, its solution, or its emulsion from a number of ELSANTM (Rhodia Agro), 1-(2-chlorobenzoyl)-3-(4- places in the particular area. Further details regarding dis trifluoromethoxyphenyl)urea ("Trifumuron"), available ruption of moth mating are disclosed in U.S. Pat. No. commercial under the name ALSYSTINTM (Bayer), and 25 3,980.771 to Meijer et al., which is hereby incorporated by abamectin, available commercially under the name VER reference. MECTINTM (Merck), are preferred. Further details respect The present invention also provides a method for attract ing these and other suitable insecticides are disclosed in ing moths to a particular location comprising providing at Worthing, ed., The Pesticide Manual, 9th Ed., British Crop the particular location about 10 picograms to about 10 Protection Council, which is hereby incorporated by refer milligrams, preferably about 1 nanogram to about 1 micro CC. gram of the moth attractants of the present invention. The invention further relates to a moth control composi Proximate to the particular location, moths attracted with the tion comprising a biocontrol agent and a moth attractant. For aforementioned method can be exposed to an agent which the purposes of the present invention, a biocontrol agent is impairs their ability to mate, thereby controlling the moth defined as any biological enemy (e.g., predator, pathogen, 35 population. Suitable moth control agents include, for parasite) of the moth. Examples of biocontrol agents include example, moth restraining devices, insecticides, biocontrol pathogenic nematodes, fungi, yeast, bacteria, and viruses. In agents, or chemosterilants, as described above. The method use, the attractant lures moths to the biocontrol agent/ of attracting moths can also be used to draw moths away attractant moth control composition where the moths are from sensitive locations to less sensitive locations, such as, infected with the biocontrol agent. The moths then return to for example, from a region where tomatoes are cultivated to the general moth population and disseminate the agent to the a region where no tomatoes are cultivated. rest of the population. As a result, an entire infestation of It is also envisioned that the moth attractants of the moths can be reduced by luring and infecting a few members present invention can be used to detect the location and of the population with the appropriate pathogen. boundaries of localized moth infestation and to monitor The biocontrol agent/attractant moth control composition 45 moth populations. Such a method can employ the traps of can be in the form of, for example, a spray, such as the present invention, placed at strategic locations within emulsifiable concentrates or wettable powders, aerosols, and near the suspected area of infestation. The quantity of dusts, baits. granular formulations, and laminated slow moths trapped at each of these strategic locations would release formulations. The attractants can be combined with permit a mapping of the boundaries of moth infestation. the biocontrol agent, without a support, and spread over the 50 Alternatively, the attractant can be placed on a support and area of moth infestation, preferably as a mist or as a dust in the number of moths approaching the support counted a suitable carrier, such as vegetable oils, refined mineral oils, electronically, optically, mechanically, or otherwise, without rubbers plastics, silica, diatomaceous earth, and cellulose trapping, restraining, killing, or otherwise incapacitating the powder. Alternatively, the attractant can be combined with moths. In this way, an estimate of the moth population the agent on a support. Suitable supports include those 55 density can be obtained. The area of localized infestation can suitable for use in moth traps, examples of which are listed then be treated with biocontrol agents or insecticides or both, above. Biocontrol agent/attractant moth control composi thus permitting efficient and directed use of such biocontrol tions on supports are advantageous, because they eliminate agents and insecticides. Further details regarding the use of the need to spread biocontrol agents unnecessarily. Because moth attractants to detect and locate areas of moth infesta the mechanism by which biocontrol agents operate requires tion are disclosed in U.S. Pat. No. 5.236,715 to McDonough return of the infected moth to the population, the support is et al... and U.S. Pat. No. 3,980.771 to Meijer et al., which are preferably used without an insecticide or moth restraining hereby incorporated by reference. member. In each of the aforementioned moth traps, moth control It is also envisioned that chemosterilants can be used in compositions, including those comprising insecticides, bio conjunction with the moth attractants of the present inven 65 control agents and chemosterilants, and methods of using tion to attract and sterilize male moths. Methods for expos moth attractants, the moth attractant referred to therein can ing moths with the chemosterilant/attractant moth control be a 3.8-tetradecadienyl acetate, a 3.11-tetradecadienyl 5,728,376 13 14 acetate, an 8, 11-tetradecadienyl acetate, a 3,8,11 T. Baker). Silver nitrate column chromatography was done tetradecatrienyl acetate, or mixtures thereof. It is preferred on silica gel impregnated with AgNO, (20% of AgNO on that the moth attractant be isolated. It is further preferred that silica gel Merck H 60). the isolated moth attractant be substantially pure. Preferably, NMR spectra were recorded on an Unity-200 ('H, 200 the 3,8-tetradecadienyl acetate is (3E,82)-3,8- MHz, Varian), on a Unity-400 (H NMR. 400 MHz, 'C tetradecadienyl acetate, the 3.11-tetradecadienyl acetate is NMR, 100.6 MHz, Varian), and on a Unity-500 ("H NMR, (3E,112)-3, 11-tetradecadienyl acetate, and the 8.11 500 MHz and 'C NMR, 125.7 MHz, Varian) as CDC1, tetradecadienyl acetate is (87.11Z)-8, 11-tetradecadienyl solutions at room temperature. Chemical shifts, given in acetate. Suitable 3.8.11-tetradecatrienyl acetates include ppm, are expressed as 8 values measured from the residual (3E.8E.11E)-3.8.11-tetradecatrienyl acetate, (3E.8E.11Z)-3. 10 CHCl signal (7.26 ppm). Vapor phase infrared spectra were 8.11-tetradecatrienyl acetate, (3E,82.11E)-3.8, 11 recorded using a Hewlett-Packard (HP)5965 AIRD coupled tetradecatrienyl acetate, (3E,8Z.11Z)-3,8,11-tetradecatrienyl to a HP 5890 GC. Electron impact (70 eV) spectra were acetate, (3Z.8E.11E)-3,8,11-tetradecatrienyl acetate. (3Z, obtained using a HP 5890 GC coupled to an ITD ion trap 8E,11Z)-3,8.11-tetradecatrienyl acetate, (3Z.8Z.11E)-3,8. detector (Finnigan). Fast atom bombardment (FAB, in a 11-tetradecatrienyl acetate, and (3Z,8Z.11Z)-3,8.11 5 glycerin matrix) mass spectra were obtained on a ZAB-Q tetradecatrienyl acetate. Preferably, the attractant includes a (VG) instrument. For GC analysis a Supelco fused-silica 3.8.11-tetradecatrienyl acetate and, more preferably, (3E,8Z. capillary column (30 mx0.25 mm) coated with SE-54 (0.25 11Z)-3,8,11-tetradecatrienyl acetate. Alternatively, the pum) fitted in a HP5890GC equipped with a flame-ionization attractant can be an attractant blend of the present invention. (FID) detector was used. Synthetic samples (about 1 mg/ml In each of the aforementioned methods of using moth 20 in hexane) were injected in split mode using a temperature attractants, including the methods of attracting moths, con program of 60° C. for 4 min, 10°C/min to 270° C. and held trolling a population of moths, disrupting mating of moths, for 20 min. Analyses of natural samples were carried out detecting the location and boundaries of localized moth using fused-silica capillary columns (0.22 mmx30 m) coated infestation, and moth sterilization, the moths referred to with free-fatty-acid phase ("FFAP") or DB-5 stationary therein are preferably Scrobipalpuloides absoluta. 25 phases (J&W Scientific. Folsom, Calif.). The present invention is further illustrated by the follow ing examples. Example 2 EXAMPLES Preliminary studies Preliminary studies on the mating behavior of S. absoluta Example 1 showed that the females attract males even on the first day after emergence. Over 50% of females (n=34) in a labora Materials and Methods tory colony showed maximum calling activity from 5:30 to S. absoluta larvae were collected from tomato plantations 7:30 AM. Bioassays conducted with calling caged females near the Federal University of Vigosa, and reared in the 35 in a wind-tunnel showed that the males respond and fly laboratory on a diet of fresh tomato leaves (Licopersicum immediately to females during this short period of time esculantum). Pupae were collected every three days and during which the females release pheromones. During the sexed as described by Coelho et al., "Biologia, quetotaxia da calling period, the females extrude the ovipositor and expose larva e descricao da pupa da traca-do-tomateiro." Pesqui. the intersegmental glandular membrane. The intersegmental Agrop. Bras, 22:129-135 (1987), which is hereby incorpo membrane ("pheromone gland") of calling females was rated by reference. Five specimens of each sex were placed excised and extracted with hexane. in glass tubes (8.0X2.5 cm) and insects of each sex were kept A preliminary examination of hexane extracts made from in a different room. All the insects were maintained at a excised pheromone-producing glands of females that were temperature of 23-2° C., under a 14:10-hr light-dark cycle. actively attracting conspecific males, using capillary gas and a relative humidity of 75.5%. After emergence, the 45 chromatography-mass spectrometry, showed the presence of females were observed during the scotophase and the begin two significant GC peaks in the region where lepidopteran ning of the photophase to recognize their calling time and pheromones usually appear, as indicated in FIG. 1. The behavior. minor constituent was partially characterized by GC/MS as Hydrazine hydrate and hydrogen peroxide (30 wt % a tetradecadienyl acetate. The mass spectrum corresponding solution in water) were purchased from Mallinckrodt to the major peak (90%) is shown in FIG. 2. From the base (Chesterfield, Mo.) and Fisher Chemical Co. (Fair Lawn, peak at m/z 43, it was apparent that this component is an N.J.), respectively. Butyllithium (1.6M and 2.5M solutions acetate, and the ion produced by loss of acetic acid, (M-60) in hexane), 2-(3-butynyloxy)tetrahydro-2H-pyran (1- at m/z 190, indicated that the compound is a tetradecatrienyl (tetrahydopyran-2-yloxy)-3-butyne), lithium acetate. A comparison of the integrated GC peak area is this tetrahydridoaluminate, borane-methylsulfide complex, 55 component with that of an external standard showed that the Cu(I)Br.MeS complex, and p-toluenesulfonyl chloride amount of this constituent obtainable from each female from Aldrich Chemical Co. (Milwaukee, Wis.), and bromine gland to be about 1-5 ng. and triphenylphosphine from Fluka Chemical Co. An attractive strategy to locate the position and configu (Ronkonkoma, N.Y.), were used as purchased. ration of the three double bonds is a partial reduction of the 1-(Tetrahydopyran-2-yloxy)-4-pentyne was prepared from material to obtain a product mixture containing all possible the corresponding alcohol using the methods described in monoene acetates, since excellent techniques are available Robertson, "Adducts of tert-alcohols containing an ethynyl for the determination of double bonds in monoenes. Partial group with dihydropyran. Potentially useful intermediates." reduction was effected by the diimide procedure described J. Org. Chem. 25:931-932 (1960), the disclosure of which by Corey et al., "Chemistry of diimide. Some new systems is hereby incorporated by reference. Column chromatogra 65 for the hydrogenation of multiple bonds." Tetrahedron Lett. phy was run on silica gel (Merck, H 60), and reactions were 1961:347-352 and Yamaoka et al., "Determination of geo monitored by TLC on Baker-flex Silica gel DB2-F plates (J. metric configuration in minute amounts of highly unsatur 5,728,376 15 16 ated termite trail pheromone by capillary gas chromatogra -continued phy in combination with mass spectrometry and fourier f E-CH2-s \ / o 1. CyzBH, 4.4 eq. transform infrared spectroscopy." J. Chromatogr., 2. CH3CO2H C 399:259-267 (1987), which are hereby incorporated by 3. 3. NaOH/H2O2 reference. The exact conditions required to carry out this two-step procedure using less than 100 ng of the starting -PPh3/Br, 1.5 eq. G material were worked out using (4Z,7Z.10Z)-4.7.10 VVVVote tetradecatrienyl acetate as a model. Once the optimal con ditions were established, the natural pheromone extract was 10 subjected to a partial diimide reduction as follows. An - / oIHP ethanol extract containing 125 female sex glands was con Br - Li-E G centrated to a few microliters and mixed with a solution of VVVV DMPUf IHF O C. hydrazine (10 ul, 10% in ethanol) and hydrogen peroxide (10 ul, 0.6% in ethanol). The mixture was heated at 60° C. 15 for 2.5 hr and allowed to cool to room temperature. It was acidified with dilute HCl and extracted with hexane (3x15 OTHP ul). The combined hexane layers were reduced to 2-3 ul and Dowe MeOH G reconstituted to 10 ul with hexane. One pil of this extract, together with hexadecane and tetracosane as internal standards, was analyzed by GC-MS. W OH LiAlH4/diglyme GC-MS analysis of the reduced mixture showed the G presence of three tetradecenyl acetates along with doubly 120-140° C. unsaturated and saturated acetates. In order to identify these three tetradecenyl acetates precisely, the mass spectra as 25 well as the GCretention times of all 23 possible tetradecenyl Ac2O/pyridine acetates on two different gas chromatographic stationary phases (DBWax, and DB-23) were measured, and these data were compared to those obtained for the three tetradecenyl acetates that resulted from partial reduction of the natural 30 pheromone. In this way, two of the monoenes derived from the natural pheromone were identified unambiguously as (E)-3-tetradecenyl acetate and (Z)-8-tetradecenyl acetate. However, retention data alone could not establish the iden tity of the third isomer, since the retention times of (Z)-11 35 tetradecenyl acetate and 13-tetradecenyl acetate were very Example 3 similar on both GC phases. To establish the identity of the third tetradecenyl acetate, the mixture was converted into a Preparation of 2-pentyn-1-yl p-toluenesulfonate (2) mixture of the corresponding dimethyl disulfide ("DMDS") Propargyl alcohol (Aldrich Chemical Co., St. Louis. Mo.) (11.8 g. 200 mmol) was added dropwise (30 min) to a adducts using the methods described in Francis et al., suspension of lithium amide in liquid ammonia (600 mL), "Alkylthiolation for the determination of double bond posi formed from lithium wire (2.8 g. 0.4 mol), followed by ethyl tion in linear alkenes." J. Chromatogr: 219:379-384 (1981), bromide (21.8 g. 200 mmol) which was added during a Buser et al., Anal. Chem, 55:818-822 (1983). and Attygalle period of 45 min. The reaction mixture was stirred for 1 hr et al., Angew. Chem. Int. Ed. Engl., 27:460-478 (1988), in boiling ammonia. Usual work-up and distillation under which are hereby incorporated by reference. GC-MS analy 45 reduced pressure afforded 2-pentyn-1-ol (14.2g, 85% yield) sis of this mixture showed the expected presence of DMDS of b.p. 63-66 C/23 torr. "H NMR (200 MHz) 8: 4.22 (bs. adduct of an 8-tetradecenyl acetate (m/z(%). 348 (M'.10), 2H, CHO-1), 2.21 (tg, J=2.2, 2.2. 2.2, 7.5, 7.5 Hz, 2H. 217(40). 131(23)), and that of an 11-tetradecenyl acetate CH-4), 1.80 (bs, 1H, OH), 1.12 (t, J-7.5, 7.5 Hz, 3H, (m/z (%).348(M'.15).259(95),89(38)). Retention times of CH-5). these two adducts on a DB-1 capillary column were identical 50 A solution of 2-pentyn-1-ol (8.40 g, 100 mmol) in THF to those obtained from the DMDS derivatives of authentic (60 mL) was treated with p-toluenesulfonyl chloride (23.9 g, (Z)-8-tetradecenyl acetate and (Z)-11-tetradecenyl acetate. 125 mmol) at -10° C., followed by pulverized KOH (11.3g, Based on these results, the triply unsaturated compound was 200 mmol) without allowing the temperature to exceed -5° identified as (3E.8Z.11Z)-3.8.11-tetradecatrienyl acetate. C. After 1.5 hours of stirring at -10°C., 50 mL of saturated 55 brine was added and the product extracted into CHCl2. The The structure and stereochemistry was further supported product, 2-pentyn-1-ylp-toluenesulphonate (2), was isolated by synthesis of (3E.8Z.11Z)-3,8.11-tetradecatrienyl acetate, by flash chromatography (18.17 g 76.4% yield). "H NMR as described below in detail with reference to the following (200 MHz) 8: 7.81 (d. J-8.4 Hz, 2H, arom. CH). 7.33 (d. reaction sequence: J=7.9 Hz, 2H, arom. CH), 4.68 (t, J=2.2, 2.2 Hz, 2H, CHO-1), 2.44 (s, 3H. arom. CH). 2.13 (ta. J-2.2.2.2.2.2. H.-E. 7.5, 7.5 Hz.2H, CH-4), 1.00 (t, J=7.5.7.5 Hz, 3H, CH-5). VA oTHP 1) EMgBr THE G Example 4 l 2)/ OTs Preparation of 1-(tetrahydropyran-2-yloxy)-4,7- 65 decadiyne (3) A solution of 1-(tetrahydropyran-2-yloxy)-4-pentyne (1) (8.40 g, 50 mmol) in dry THF (30 mL) was treated with 5,728,376 17 18 CHMgBr in THF (30 mL) which was freshly prepared temperature for 20 min. Into the slightly yellow suspension from ethyl bromide (5.99 g, 55 mmol) and magnesium (1.58 that formed, the crude mixture of 4 and 4Z,7Z)-4,7- g, 66 mmol). After intensive evolution of ethane decreased, decadien-1-ol (12.4 g) in CHCl (15 ml) was added drop the mixture was refluxed at 60° C. for 1 hr. The solution was wise. After stirring for 1 hour, a solution of saturated transferred into a suspension of Cu(I)Br.MeS complex NaHCO (50 mL) and water (50 ml) were added. The (0.51 g, 5 mol%) in dry THF (50 mL). The solid dissolved mixture was extracted with pentane and combined extracts gradually and formed dark solution which was stirred at were stored overnight in a freezer. In this way, triph room temperature for 20 min. The mixture was cooled on an enylphosphine oxide could be crystallized and removed by ice bath and a solution of 2 (8.4g, 35 mmol) in dry THF (10 filtration. Column chromatography followed by distillation mL) was added dropwise during 30 min. After an additional at reduced pressure afforded 5 (3.48g, 32% yield based on 1 hr on the ice bath, the mixture was stirred at room 1 of bp. =80°-85° C./2.5 torr. "H NMR (200 MHz) 8: 5.37 temperature for 12 hr. The reaction was quenched with a (m, 4H, CH=CH), 3.41 (t, J-6.6, 6.6 Hz, 2H, CH-Br), solution (50 mL) containing 1:2 (v/v) mixture of concen 2.80 (dd, J-6.4.6.5 Hz, 2H. =CH-CH-CH=). 2.21 (dt, trated aqueous ammonia and saturated NHCl solution. The J=7.0, 6.9, 6.8, 6.9 Hz, 2H. CH-3), 2.07 (dq, J-7.4 Hz, usual work-up afforded a crude product (11.6 g), containing 15 CH-9), 1.91 (tt, J=6.7. 6.6.7.0, 7.0, 2H, CH-2), 0.97 (t, 98% of the desired product (3) and 2% of the tosylate. "H J=7.5, 7.5 Hz, 3H, CH). CNMR (100.6 MHz) 8: 132.1 NMR (200 MHz) 8: 460 (m. 1H, CH-2), 3.82 (m, 2H, (8), 129.8 (5), 127.6 (7), 127.0 (4), 33.4 (1). 32.5 (2), 25.6 CH-6 and 1), 3.45 (m,2H, CH-6 and 1), 3.10 (dt, J=4x2.3 (3), 25.5 (6), 20.6(9), 14.3 (10). MSEI, m/z (%) 218 (M', Hz, 2H, =CH-CH-CH=), 2.28 (m. 2H, CH-3), 2.16 15), 216 (17), 137 (6), 109 (13), 107 (18), 96 (14), 95 (78). (td.J=7.6, 2.3.2.4, 7.6.7.6 Hz, 2H, CH-9), 1.8-1.4 (m, 8H, 82 (18), 81 (74), 79 (22), 68 (27), 67 (100), 55 (17), 53 (15), CH-2, -3', -4', and -5). 1.11 (t, J=7.6, 7.6 Hz, 3H, CH-10). 42 (11), 41 (38), 40 (40). 'CNMR (100.6 MHz) 8: 98.7 (2'), 81.8 (7), 79.7 (5), 74.7 (8), 68.4 (4), 66.6 (1), 62.1 (6'). 30.7 (3'). 28.9 (2), 25.5 (4), Example 7 19.5 (6), 15.7 (5'), 13.9 (3), 12.4 (9), 9.7 (10). Preparation of (82.11Z)-1-(tetrahydropyran-2- 25 Example 5 yloxy)-8.11-tetradecadien-3-yne (6) A solution of 1-(tetrahydropyran-2-yloxy)-3-butyne (2.25 Preparation of (4Z.7Z)-1-(tetrahydropyran-2-yloxy)- g, 14 mmol) in dry THF (15 ml) was treated at -50° C. with 4.7-decadiene (4) n-butyllithium hexane solution (11 ml, 17.5 mmol). After 15 An ice-cooled solution of cyclohexene (24 ml, 240 mmol) 30 minat -30°C., the mixture was kept at room temperature for in dry THF (50 ml) was treated with aborane-methylsulfide 30 min. The mixture was then treated at 0°C. with 5 (3.0 g. complex solution in toluene (60 ml, 120 mmol) for 20 min. 13.8 mmol) dissolved in 1,3-dimethyl-3,4,5,6-tetrahydro-2 After an additional 20 min of stirring on an ice bath, the (1H)-pyrimidine (DMPU) (15 mL) during 30 min. The resulting suspension was stirred at room temperature for 2 reaction mixture was stirred 12 hr. at room temperature and hr. This dicyclohexylborane slurry was treated with a solu 35 quenched with saturated NHCl solution (30 ml). The prod tion of 3, prepared in Example 4, (11.6 g., 49.8 mmol) in dry uct (6) was removed with ether (3x50 ml) and purified by THF (50 mL) at 0°C. After 12 hr at room temperature, the silica-gel flash chromatography (2.2g, 55% yield). "HNMR mixture was treated with glacial acetic acid (40 mL) at 0°C., (200 MHz) 85.36 (m, 4H, CH=CH), 4.64 (m. 1H, CH-2), and stirred for 7 hr. The mixture was made basic with 5M 3.81 (m.2H, CH-6' and 1), 3.54 (m.2H, CH-6 and 1), 2.78 NaOH, and carefully oxidized with HO (30%, 40 ml) for (dd, J-6.0, 6.0 Hz, 2H. =CH-CH-CH=), 2.47 (m, 4H, 1 hr. The reaction products were extracted into ether, and CH-2, and -5), 2.15 (m, 4H. CH-7, and -13), 1.8-1.4 (m, cyclohexanol was distilled off using a Vigreux column under 8H, CH-6, -3', 4', and -5'), 0.96 (t, J-7.5, 7.6Hz.3H, CH). reduced pressure. Finally, 12.4 g of a crude oil was isolated 'C NMR (100.6 MHz) 8: 131.8 (12), 128.9 (9.11), 127.2 which was shown by GC analysis to consist of a 1:1 mixture (8), 98.7 (2), 81.0 (3), 76.6 (4), 66.2 (1), 62.2 (6), 33.4 (2), of 4 and (4Z.7Z)-4,7-decadien-1-ol. 4. "H NMR (200 MHz) 45 30.6(3'), 28.9 (7), 26.2 (6), 25.5 (14), 25.4 (4"). 20.5 (5). 20.2 8: 5.38 (m, 4H, CH=CH-4, -5,-7, and -8), 4.57 (m. 1H, CH (13). 18.3 (5'), 14.3 (10). MSEI, m/z (%), 159 (7), 131 (9). -2'), 3.72 (m,2H, CH2-6' and 1), 3.41 (m.2H, CH2-6' and 1), 119 (8), 117 (9), 105 (8), 93 (11).91 (16), 86 (12), 85 (100). 2.77 (dd, J-5.6, 2.8 Hz, 2H, =CH-CH-CH=). 2.13 (m. 79 (18), 77 (11), 67 (36), 57 (16), 55 (15), 43 (29), 42 (16). 4H, CH-3, 9), 1.8-1.4 (m, 8H, CH-2, -3', -4', and -5'), 0.96 41 (51), 40 (24). (t, J=7.5, 7.5 Hz, 3H, CH,-10). MS (EI, m/z (%) 169 (5), 50 Example 8 153 (7). 135 (5), 123 (5), 109 (7), 95 (10), 85 (100), 67 (18). MS (FAB, m/z) 237 (M-1). Preparation of (87.11Z)-8, 11-tetradecadien-3-yn-1- 4Z,7Z)-4,7-decadien-1-ol. "H NMR (200MHz) 85.37 (m. ol (7) 4H, CH=CH-4, 5, 7, 8). 3.64 (m, 2H, CH-1), 2.77 (dd, 55 Asolution of 6 (2.2g, 7.5 mmol) in methanol (50 mL) was J=5.1, 5.7 Hz, 2H. =CH-CH-), 2.10 (m, 4H. CH-3, stirred with DOWEXTM 50W-X8 (Dow Chemical, Midland, and -9), 1.64 (tt, J=6.5, 6.6.7.0, 7.5 Hz, 2H, CH,-2), 0.96 (t, Mich.) ion exchange resin (2 g) and the formation of 7 was J=7.5, 7.5 Hz, 3H, CH). 'CNMR (100.6 MHz) 8: 1319 monitored by TLC. The resin was removed by filtration and (8). 129.1 (5), 128.8 (7), 127.1 (4), 62.5 (1). 32.7 (2), 25.5 washed with methanol (3x20 mL). The alcohol 7 was (6), 23.5 (3), 20.5 (9), 14.3 (10). purified by flash chromatography (1.3 g 83% yield). "H NMR (200 MHz) 8: 5.36 (m, 4H, CH=CH), 3.66 (t, J=6.1. Example 6 6.4 Hz, 2H. CH-1). 2.78 (t. J=6.4, 6.7 Hz. 2H, =CH CH-CH=), 2.42 (tt, J=2.1, 24., 6.1, 6.4 Hz, 2H, CH-2), Preparation of (4Z.7Z)-1-bromo-4,7-decadiene (5) 2.16 (tt, J-2.1, 2.4, 7.0, 7.3 Hz, 2H, CH-5), 2.15 (m. 2H, A solution of triphenylphosphine (20.9 g, 80 mmol) in 65 CH-7), 2.06 (dq, J=7.3.7.0, 7.3.7.6 Hz, 2H, CH-13), 1.55 CHCl (100 ml) was treated with Br (7.8 g. 49 mmol) in (tt, J=7.1, 7.3, 7.3, 7.3 Hz, 2H. CH-6), 0.96 (t, J=7.3, 7.6 CHCl (15 mL, 0°C.) and the mixture was stirred at room Hz, 3H, CH,-14). 'C NMR (100.6 MHz) 8: 1319(12), 5,728,376 19 20 129.0(11), 128.8(9), 127.2(8), 82.3(3), 76.6(4), 61.3(1), 28.8 responses at all concentrations of the pheromone that was (7), 26.2(6), 25.5(10), 23.1(5), 20.5(2), 18.2(13), 14.2(14). tested. For example, males showed induced wing fanning, MS EI, m/z(%) 161(15), 159(20), 145(30), 133(25), 131 oriented flight, and landing on the source of the synthetic pheromone, even at the 10 ng level, the lowest amount (27), 119(34), 117(42), 105(42), 95(17), 93(27), 91 (83), tested. Naturally, the control dispensers loaded only with 79(76), 77(37), 69(22), 67(78), 65(29), 55(46), 53(39), hexane did not induce any significant behavioral responses. 44(29), 43(24), 42(34), 41(100), 40(61). Highest responses were observed at the 1000 ng level. At this concentration, 100% of the test insects (N=30) showed Example 9 wing fanning, and 87% initiated an oriented flight toward the dispenser with 83% landing on the dispenser. The corre Preparation of (3E.8Z.11Z)-3,8,11-tetradecatrien-1- O sponding responses obtained by using nine calling females y1 acetate (9) as the pheromone source were 38, 66, and 61%, respectively. A solution of 7 (0.4 g. 1.94 mmol) in dry diglyme (6 ml) The results in FIG. 3 indicate that a dispenser loaded with was added slowly to a suspension of LiAlH4 (0.228 g, 5.7 1000 ng of the synthetic pheromone 9 is thoroughly com mmol) in dry diglyme (4 mL) at room temperature. The petitive with the attractivity of a group of nine calling mixture was refluxed at 120°-140° C. for 5 hr and then 15 females. cooled in an ice bath. Ethyl acetate (5 ml) was carefully Example 11 added, and the mixture was poured into an ice and conc. HCl mixture (10 ml). Extraction with ether followed by flash Field Tests chromatography afforded the alcohol (8) (0.225 g), which These experiments were carried out at a 20-ha tomato was acetylated with acetic anhydride (1 mL) and pyridine (3 20 (Sata Clara variety) plantation in Araguari (State of Minas mL) for 1 hr. Flash chromatography, and purification on 20% Gerais, Brazil) from Apr. 1, 1994, to Apr. 11, 1994. The traps AgNO-impregnated silica gel afforded the desired product were placed at a height of 1.20 m, and at 30-m intervals as (3E.8Z,112)-3,8,11-tetradecatrien-1-yl acetate (9) (0.238 g), suggested by Uchöa-Fernandes et al. In Congresso 50% yield based on (87, 11Z)-8.11-tetradecadien-3-yn-1-ol Brasileiro de Entomologia, Recife/PE, 13:639 1991) and (7). H NMR (400 MHz) 8: 5:50 (dtt, J-15.2, 6.4., 6.4, 2.3, 25 Uchóa-Fernandes et al., "Field trapping of the tomato worm, 2.4 Hz, 1H, trans=CH-3), 5.36 (m, 5H, CH=CH), 4.06 (t, Scrobipalpuloiodes absoluta (Meyrick) (Lepidoptera: J=6.7, 7.0 Hz, 2H, CH,-1), 2.77 (dd, J=5.2, 6.8 Hz, 2H, Gelechiidae) using virgin females." Ann. Soc. Entomol. =CH-CH-CH=), 2.31 (dt, J=2.3, 6.8, 7.0 Hz, 2H, Brasil, 23:271-276 (1944), which are hereby incorporated CH-2), 2.06 (m, 6H, CH-5, -7. and -13), 2.04 (s, 3H, 30 by reference. COCH,), 1.42 (tt, J=7.3, 7.3, 7.6, 7.6 Hz.2H, CH-6), 0.97 The first series offield experiments used five different trap (t, J=7.3,73 Hz,3H, CH). 'CNMR (100.6 MHz) 8: 171.1 designs, depicted in FIGS. 4A-4E. Trap A was made from (1"), 133.2(4), 131.8(12), 129.7(9), 128.3(11), 127.3(8). white cylindrical PVC tubing (20 cm diameterx25 cm). Trap 125.4(3), 64.1(1), 32.1(2), 319(6), 29.3(7), 26.6(5), 25.6 B was similar to Trap A; however, the cylinder was split into (10), 21.0(2), 20.5(13), 14.3(14). MS(EI, m/z(%) 190(M" 35 two halves and the two parts were connected with four metal -60, 4), 161(9), 133(13). 119(9), 108024), 107(15). 105(10), wires to form two parallel 5-X-25 cm openings on both sides. 93(54), 91(22), 80(43), 79(91), 67(68), 55(29), 43(100). Trap C was a delta type with a maximum vertical gap of 41(45). IR (gas phase, cm) 3017 (cis-C-H str), 2936 7-cm at the triangular opening, and a base area of 29x30 cm. (CH) 1761 (C=O), 1231. 1037 (C-O-), 967 (trans= The bottoms of traps A.B. and C were lined with removable C-H wag). sticky paper to catch insects. Trap D was made from a plastic tray (24X37x6 cm), to which an inverted V-shaped hood was Example 10 attached with four metal rods. This house-shape trap was open from all four sides with a 8-cm opening at the mini Wind Tunnel Experiments mum and 15-cm gap at the maximum opening in the middle. Synthetic samples of acetate 9 were applied as pentane 45 Trap E was made from two 20- and 32-cm diameter black solutions to rubber septa (cleaned by washing with dichlo plastic plates with 2-cm vertical sides, joined at three points romethane for 20hr in a soxhlet apparatus) which were used with strong metal wire to form a cage. Moth traps D and E as baits in the wind tunnel. The attractivity of each bait, contained water in the bottom plate with a few drops of a loaded with 10, 100, 1000, and 10,000 ng of acetate 9, was neutral detergent to catch insects. Rubber septa loaded with compared to that of 9 calling virgin females (1- to 4-day-old) 50 1 ug of acetate 9 were hung inside all traps as baits, and the in a cage. The control baits were treated with 100 pil of number of insects caught in each trap (N=15) was counted hexane. The wind tunnel (3.8 mx0.50 m) was operated at a each day. flux speed of 30 cm/sec. The landing platform was 1 m away The results are presented in FIG. 5. While all traps caught from the "take-off" platform. For each experiment, 3 males a large number of S. absoluta males, designs D and E, which (1- to 3-day-old; Hickel et al., "Comportamento de chama 55 were open from all directions and used water containing a mento e aspectos do comportamento de acasalamento de little detergent as the restraining agent, were much more Scrobipalpula absoluta (Lepidoptera: Gelechiidae), sob efficient than traps A, B, and C. The most efficient design condicoes de campo, An. Soc. Entomol. Brasil. 20:173-182 was trap E; a total number of 12.166 males was caught in (1991), the disclosure of which is hereby incorporated by one night in fifteen of these traps baited with dispensers reference) were placed on the "take-off" platform, and their loaded with 1 ug each of acetate 9. behavioral responses were observed for 5 min and catego In the second series of experiments (20 replications). rized as follows: 1=no response, 2-wing fanning, 3=none rubber baits loaded with 1, 10, and 100 g of acetate 9, or oriented flight, 4-oriented flight, and 5=landing on the 100 pil of hexane, were used in E type traps. For comparison. source. The test was repeated 10 times for each concentra a one-day-old virgin female in a cylindrical cage (4X4 cm) tion, 65 with the open ends covered by nylon mesh, was hung inside The results are presented in FIG. 3. The males placed on an E type trap. The number of males caught per trap was the "take-off" platform showed significant behavioral counted each morning. 5,728,376 21 22 As the results presented in FIG. 6 show, all baited traps -continued attracted very large numbers of S. absoluta males, proving OTMS (CH3(CH2)NF/THF further that (3Z.8Z.11Z)-3,8.11-tetradecatrienyl acetate (9) VVVVVV is a potent attractant. The number of males caught per trap gradually increased as the amount of pheromone loaded on the dispensers increased. The traps baited with 100 g of 9 caught, on average, 1200 males per trap per night, while Ac2O/pyridine those baited with one one-day-old virgin female caught only v-v-v" “T’ 201 males. Even the traps baited with 1 ug of 9, which caught about 535 males per trapper night, were observed to O 13 compete well with virgin females in terms of attracting OCOCH3 males in the field. Control traps having dispersers loaded only with hexane caught on average about 20 males per trap per night. 4 In the third series of experiments, two C type delta traps 15 with sticky bottoms (27x20 cm) were baited with 1 g of Magnesium turnings (30 mg, 1.28 mmol) were warmed acetate 9. For a period of 24 hr, the number of males caught per trap at the end of each one hour period was counted, and (with a heating gun) and stirred for 1 hr under argon. The the sticky cards were replaced when necessary. turnings were covered with dry THF (100 l), and ten drops From the results of the third series of field tests, presented of a solution of 4Z.7Z)-1-bromo-4,7-decadiene (5) (200 mg. in FIG. 7, it is evident that the males of this species have a 0.925 mmol), prepared according to Example 6, in dry THF very distinct time period in which they actively search (3 ml) were added. The mixture was brought to reflux, and calling females. Appropriately baited traps caught an aver after the reaction started, the remaining solution of 5 was age of 240 males/trap during the period of 6:00 to 7:00 AM. added dropwise at 0°C. over a period of 1.5 hr. The mixture Many fewer males were caught from 7.00 to 8.00 AM. 25 was then stirred for 2 hr at room temperature to form the However, the numbers caught became negligible after 8.00 Grignard reagent (10). AM. Since no males were caught before 5 AM or after 10 AM, data for the remainder of the 24-hr time period are not Dry THF (3 ml) was treated with trimethylsilyl iodide included in FIG. 7. (260 mg, 185ul, 1.30 mmol) at room temperature and stirred 30 for 15 min to form 4-trimethylsiloxybutyl iodide (11). A Example 12 solution of CuCN. (LiCl) in THF (1M, 100 ul) was added, and the mixture was cooled to -40°C. The above prepared Preparation of (87.11Z)-8, 11-tetradecadienyl acetate solution of Grignard reagent 10, was then added over a (14) 35 period of 30 min, and a white precipitate formed. The (8Z.11Z)-8.11-tetradecadienyl acetate was synthesized as mixture was stirred at -40° to -20° C. for 1 hr followed by described in detail below with reference to the following an additional 1 hr at room temperature. The reaction was reaction sequence: quenched with ammonium chloride solution and ammonia mixture (2:1, viv), and the product was extracted with H hexane/ether (1:1) mixture (R-060, 19:1 hexane/ethyl OTHP 1) EMgBr IHF G acetate, viv). The crude (82.11Z)-trimethylsiloxy-8.11 l / = \ OTs/ tetradecadiene (12) was dissolved in THF (6 ml) and depro Cu(I)BriMe2S tected with tetrabutylammonium fluoride solution in THF -20° C.O C. 45 (1M.2 ml) to form the alcohol 13. Acetylation of the alcohol 13 with acetic anhydride/pyridine mixture (0.1 ml/1 ml) and M E-CH33. - VA 1. CyzBH, 4.4 eq. purification by flash chromatography afforded (87.11Z)-8, OTHP for Se 11-tetradecadien-1-yl acetate (14) (80 mg) in 34% yield 3. 3. NaOHAHO. based on the starting bromide (5). "H NMR (400 MHz) 8: 50 O 5.36 (m, 4H, CH=CH-8, 9, 11, 12), 4.05 (t, J=6.7, 7.0 Hz, THP CHCl 2H, CH-1), 2.77 (dd, J=64., 6.4 Hz, 2H. =CH-CH CH=), 2.06 (m, 4H. CH-7, 13), 2.04 (s.3H, -COCH), 4. 1.60 (tt, J-7.3, 7.3.7.6.7.6 Hz, 2H, CH-6), 1.4-1.2 (m, 8H, Mgether G CH-2, 3, 4, 5), 0.97 (t, J=7.3.7.6 Hz, 3H, CH-14). 'C Br e 55 NMR (100.6 MHz) 8: 171.2 (C=O), 131.7 (=CH-12), VFVFV 0-5°C. 130.0 (=CH-11). 128.0 (=CH-9), 127.3 (=CH-8), 64.6 5 (CH-1), 29.5 (CH-2), 29.1 (CH-3, 4), 28.6 (CH-5), 27.2 OTMS, (CH-6), 25.9 (CH-7), 25.5 (CH-10), 21.0 (CHC-FO), W 20.5 (CH-13), 14.3 (CH). MS (EI, m/z(%), 252 (M.2), 209 (M-43, 1), 192 (M-60.23), 163 (4); 149 (8). 135 (14), CuCNLCI 121 (38), 110 (19), 107 (19), 95 (39), 93 (40), 82 (26), 81 11 (57), 79 (66), 67 (100), 55 (38), 43 (93), 41 (50). IR (gas v-v-v - c. phase, cm) 3017 (cis-C-H str), 2936 (CH), 1761 65 (C=O), 1233, 1040 (-O-). (3E,82)-3.8-tetradecadienyl 10 acetate was synthesized as described in detail below with reference to the following reaction sequence. 5,728,376 23 24 (0.43 g) was obtained in 85% yield. GC (Rt): starting H-E-A material 15, 22.18 min, 0.4%; desired product 1621.59 min, 1Y n-BuLi/hexane OTHP Br 97.9%; the 4E isomer of 16, 21.75min, 1.7%. "H NMR (200 MHz) 8: 5.37 (m, 2H, CH=CH-4.5), 4.58 (m, 1H, CH-2'), 1. 2)/W , DMPU, or c. 3.60 (m, 4H, CH-1, 6); 2.12 (M,2H, CH-6); 2.04 (m. 2H, CH-3); 1.16 (tt, 2H.J=6.8, 6.8, 7.0.7.0 Hz, CH-2), 1.4-1.9 W VV OTHP P2-N/H. e (m, 6H, CH-3', 4'. 5"), 1.29 (m, 6H, CH-7, 8, 9); 0.88 (t. 3H. J-7.0 Hz. CH). IR (CC1 cm) 3007, 1653, 1201. 15 1138. 1120 1034. MS FAB, m/z(%) 239 (M-1), 85 (100). OTHP P(Ph)/Br, 1.5 eq. G) 10 WW CHCl, O C. Example 15

16 Preparation of Z-1-Bromodec-4-ene (17) To an ice-cool solution of triphenylphosphine (0.72 g, 15 2.74 mmol) and bromine (0.41 g, 2.6 mmol) in CHCl2, a Br Li-E / or solution of (4Z)-1-(tetrahydropyran-2-yloxy)-4-decene (16) AVVW DMPU/THF, 0° C. S (0.41 g, 1.71 mmol), prepared according to Example 16, in methylene chloride was added dropwise. Isolation and puri 17 fication by conventional means afforded the product 17 in OTHP 20 90% yield (0.33 g). "H NMR (200 MHz) 8: 5.42 (ditt, J=11.0, 7.0, 7.0, 1.0, 1.0 Hz, 2H, CH=CH-4, 5); 3.41 (t, wV DoweX/MeOH G J=6.6, 6.6 Hz, 2H CH-1, 2.20 (dt, J=7.0. 7.0 Hz, 2H, CH,-3); 2.04 (dr. J=6.5. 6.5 Hz, 2H, CH-6); 1.91 (tt, J-6.5, 18 6.5, 6.5 Hz, 2H, CH-2); 1.30 (m, 6H, CH-7, 8.9); 0.89 (t, 25 J=7.0 Hz, CH,). MSEI, m/z(%)) 220 (M*-8), 218 (M',8), OH 164 (12), 162 (12), 150 (23), 148 (23), 135 (8). 109 (12), 97 (44), 95 (14), 83 (55), 82 (14), 81 (37), 79 (15), 70 (21), 69 wVa- 120-140Audigye C. (100). 67 (39), 56 (29).55 (93). 54 (20), 43 (21), 42 (20), 41 (92), 39 (30). IR (CC1 cm) 3008 (cis CH=CH), 1246 19 30 (RCHCH-Br). 649,566 (C-Br). OH ACO/pyridi2U/pyri s Example 16 MW Preparation of (82)-1-(tetrahydropyran-2-yloxy)-8- 20 tetradecen-3-yne (18) 35 OCOCH3 1-(tetrahydropyran-2-yloxy)-3-butyne (0.30 g, 1.94 AWVVM mmol) was metallated at 0°C. with n-butyllithium (2.0M) hexane solution (1.0 ml, 1.0 eq.). The lithium acetylide that 21 formed was alkylated with the bromide 17 (0.20 g, 0.92 mmol), prepared according to Example 15, using 1,3- dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidine ("DMPU”) Example 13 as the base. This reaction afforded 214 mg of the desired Preparation of 1-(tetrahydropyran-2-yloxy)-4 product 18. However, the product was contaminated with decyne (15). 0.05 g (29%) of nonpolar impurities, identified as (87)-1.8- 45 tetradecadien-4-yne and 1-tetrahydropyran-2-yloxy)-3- 1-(Tetrahydopyran-2-yloxy)-4-pentyne (1) (0.66 g. 3.90 butyne (28%), one of the starting materials. These impurities mmol) was metallated with n-butyllithium solution (2.5M) were removed from compound 18 by repeated column in hexane (1.87 ml, 1.2 eq.). Addition of a solution of chromatography. "H NMR (200 MHz) (188: 5.35 (ditt, n-pentyl bromide (0.725 ml, 1.5 eq.) in DMPU (2 ml) J=11.0, 7.0, 7.0, 1.0, 1.0 Hz, 2H, CH=CH-8, 9), 4.64 (m, produced 0.54 g (58% yield) of the title compound (15). "H 50 1H, CH-2'), 3.58 (m, 4H, CH-1, 6'). 2.46 (tt, J=7.5, 7.5.2.5. NMR (200 MHz) 8: 460 (m, 1H, CH-2'), 3.65 (m, 4H, 2.5 Hz, 2H, CH-2). 2.14 (tt, J=7.0. 7.0.2.5. 2.5 Hz, 2H, CH-1, 6), 2.26 (tt, J=7.0, 7.0.2.0.2.0 Hz, 2H, CH-3), 2.13 CH-5). 2.10 (m. 2H. CH-7), 2.04 (dt, J-6.5, 6.5, 7.0 Hz, (tt, J=70, 7.0, 2.5, 2.5 Hz, 2H, CH-6), 1.77 (tt, J=6.8, 6.8. CH-10), 1.29 (m, 6H, CH-11, 12, 13), 1.9-1.4 (m, 8H, 7.077.0 Hz, 2H. CH-2), 1.33 (m, 6H, CH-7, 8,9). 1.52 (m, CH-6, 3', 4', 5'), 0.89 (t, J=7.0 Hz, 3H, CH). MS (EI. 6H, CH-3', 4',5'), 0.89 (t, J=7.0 Hz, 3H, CH,). MS (FAB, 55 m/z(%) 18 133 (12), 107 (10), 85 (100), 67 (15), 55 (8). m/z(%) 237 (M-1), 85 (100). IR (CC1 cm) 2229, 1322. MS (FAB, m/z) 293.2 (M). IR (CC1 cm) (18) 3007 1331, 1201, 1138, 1121, 1034. (cis-CH=CH). 2232 (acetylenic). 1403, 1201, 1184, 1137, 1122, 1034 (CH-O-). Example 14 "H NMR (200 MHz) (8Z)-1.8-tetradecadien-4-yne) 8: 5.78 (ddt, J-22.5, 10.5.2.2, 2.2 Hz, 1H, =CH-2). 5.54 (dd. Preparation of 1-(tetrahydropyran-2-yloxy)-4-decen J=22.5, 2.7 Hz, 1H, =CH-1a), 5.36 (dd, J-10.5, 2.2 MHz, (16). 1H, CH-1b). 5.36 (dtt, J-11.0, 7.0. 7.0, 1.0. 1.0 Hz, 2H, 1-(Tetrahydropyran-2-yloxy)-4-decyne (15) (0.5 g. 2.1 CH=CH-8, 9), 2.31 (dt, J=2.1, 7.3, 7.3 Hz, 2H, CH-5), mmol), prepared according to Example 13, was hydroge 2.15 (dt, J-7.0. 7.3. 7.3 Hz, 2H, CH-10). 2.03 (dt, J=6.4. nated in ethanol (20 ml) over P2-Ni, formed from nickel 65 6.4., 6.7 Hz, 2H, CH-7), 1.59 (tt, J=7.0, 7.0, 8.0, 8.0 Hz, 2H, acetate (75 mg) deactivated with ethylenediamine (0.2 ml) CH-6), 1.30 (m, 6H. CH-11, 12. 13), 0.89 (t, J=7.0 Hz, for 4 hr. After chromatography on silica gel, the product (16) CH). 'C NMR (CDCl3) (8Z)-1,8-tetradecadien-4-ynel 8: 5,728,376 25 26 131.1 (=CH-9), 1264 (=CH-8), 125.5 (=CH-1), 117.6 acetate (30) was prepared by a synthetic route similar to that (=CH-2).90.9 (=C-4), 79.5 (=C-3), 31.5 (CH-12), 29.4 used for the preparation of (3E.8Z)-3,8-tetradecadien-1-yl (CH-10), 28.7 (CH-7), 27.2 (CH-11), 26.3 (CH-6), 22.6 acetate (21), as depicted in the following scheme. (CH-5), 18.8 (CH-13), 14.1 (CH-14). MS EI, m/z(%) (82)-1.8-tetradecadien-4-yne) 161 (M*-29, 5). 133 (35), 5 119 (25), 105 (50), 91 (100), 79 (35), 67 (30), 41 (50). IR (CC1 cm) (8Z)-1,8-tetradecadien-4-yne) 3101 (=CH), WVVOTHP DMPUsite 0° C. 3009 (cis-=CH=CH and =CH-), 2227.2206 (acetylenic), Br 1833,972, 913 (vinyl). 22 1O Example 17 Preparation of (Z)-8-tetradecen-4-ynol (19) Tetrahydropyranyl ether 18, prepared in accordance with Example 16, was deprotected with DowexTM 50W-X8 (Dow 15 Chemical, Midland, Mich.) (40 mg) to form the alcohol. 19 (107 mg, 56% yield based on the starting bromide 17). "H NMR (200 MHz) 8: 5.35 (dtt, J-11.0, 7.0, 7.0, 1.0, 1.0 Hz, 2H, CH=CH-89).3.68 (dt, J=6.5, 5.6, 5.6 Hz, 2H, CH-1), 2.44 (tt, J=6.5, 6.5, 2.5.2.5 Hz, 2H, CH-2), 2.17 (tt, J=7.0, 7.0.2.5.2.5 Hz, 2H, CH-5), 2.12 (m. 2H, CH-7), 2.04 (m, r OTHP G 2H, CH-10), 1.76 (bt, J=6.5, 6.5 Hz, 1H, OH), 1.55 (tt, DMPU/THFO C. J=4x7.2 Hz, 2H, CH-6), 1.30 (m, 6H, CH-11, 12, 13), 0.89 (t, J=7.0Hz,3H, CH). MSEI, m/z (%) 179 (M-29.8), 163 (21), 151 (15), 133 (53), 121 (38), 107 (87), 95 (66(.93 (66), 25 91 (80), 81 (66), 79 (88), 67 (87), 55 (100), 41 (100), 29 OTHP Dowe/MeOH (29). IR (CCI, cm) 3636, 3588 (OH), 3006 (cis CH=CH). 2227 (acetylenic), 1654 (C-O) H LiAlH/diglyrne Example 18 30 120-140 C. Preparation of (3E.8Z)-3,8-tetradecadien-1-yl ACO/pyridine acetate (21) OH Al-Prime (8Z)-Tetradecen-4-ynol (19) (21 mg 0.1 mmol), prepared according to Example 17, was reduced with lithium tetrahy 35 drialuminate (20 mg, 0.5 mmol) in dry diglyme (0.5 ml) at 120° C. for 3 hr. The alcohol (20) that was formed was OCOCH acetylated with acetic anhydride (0.1 ml) and dry pyridine AMV (0.5 ml), and the product was purified on silver-nitrate (20%) 30 impregnated silica gel. This procedure afforded 18 mg (72% yield) of 21 having 97% isomeric purity. "H NMR (500 MHz) 8: 5.51 (ditt, J-15.3, 6.8, 6.8, 1.2, 1.3 Hz, 1H =CH The yield was 15% (17 mg; 96% isomeric purity (GC) -3). 5.38 (ditt, J-15.2, 6.6, 6.6, 1.2, 1.2 Hz, 1H, =CH-4). based on the starting material, 1-bromo-6-(tetrahydropyran 5.35 (dtt J-11, 6.8, 6.8, 1.2, 1.2 Hz, 2H, CH=CH-8, 9), 2-yloxy)hexane (22). "H NMR (500 MHz) 8: 5.51 (ditt, 4.07 (t, J=6.9, 6.9 Hz, 2H, CH-1), 2.31 (dtdt, J=3x6.8, 45 J=15.1, 6.8, 6.8, 1.2, 1.5 Hz, 1H =CH-3), 5.35 (m, 3H, 3x1.2 Hz, 2H, CH-2), 2.01 (tt, J-4x7.0 Hz, 6H, CH-5, 7, CH=CH-4, 11, 12), 4.06 (t. J=6.8, 6.8 Hz, 2H, CH-1), 2.31 10), 2.04 (s.3H, COCH), 1.60-1.20 (8H.m. CH,-6, 11, 12, (dddt, J=1.2.1.2, 6.8, 6.8, 6.8 Hz, 2H, CH-2). 2.05 (s.3H, 13), 0.88 (t, J=7.0. 7.0 Hz, 3H, CH,). ''C NMR (125.7 COCH). 2.02 (m, 6H, CH-5, 10, 13), 1.36-1.24 (m, 6H, MHz) 8: 171.1 (C=O), 133.3 (=CH-3), 130.3 and 129.4 CH-6, 7.8, 9), 0.95 (t, J=73, 7.6 Hz, 3H, CH,). CNMR (=CH-8, 9), 125.3 (=CH-4), 64.1 (CH-1); 32.2 (CH-2), (100.6 MHz) 8: 171.1 (C=O). 133.6 (=CH-3), 131.6 32.0 (CH-6), 31.5 (CH-12). 29.4 (CH-7, 10), 27.2 (CH (=CH-12), 1293 (=CH-11), 125.0 (=CH-4), 64.1 (CH 11), 26.6 (CH-5), 22.5 (CH-13), 21.0 (COCH), 14.1, 1), 32.6 (CH-2), 31.9 (CH-6), 29.7 (CH-8). 29.3 (CH-7). (CH-14). MSEI, m/z(%), 252 (M', 0.5), 192 (M*-60, 12), 29.1 (CH-9), 29.0 (CH-10), 27.1 (CH-5), 21.0 (COCH), 163 (5). 138 (19), 124 (20), 121 (41), 107 (19), 95 (34,93 20.5 (CH-13). 144 (CH,-14). MSEI, m/z(%) 192 (M- 55 60, 6), 163 (6), 149 (9), 135 (12), 121 (16), 107 (16), 96 (28), (34). 82 (41, 80 (100, 79 (63, 67 (60), 55 (36), 43 (100), 41 95 (37), 93 (25), 82 (50), 81 (60). 80 (35), 79 (36), 69 (33) (41). IR (CCI, cm) 3006 (cis-C-H str), 1743 (=O). 68 (64), 67 (97), 55 (45), 43 (100), 41 (67). IR (CC1 cm) 1653 (CH=CH), 1403. 1238, 1035 (C-O), 969 (trans 3006 (=CH cis str), 1743 (C=O), 1238, 1036 (C-O),969 CH=CH wag). IR (gas phase, cm) 3011 (cis-C-H str), (=CH trans wag). IR (gas phase, cm) 3012 (cis =C-H 2934 (CH2). 1761 (C=O), 1231, 1037 (-O-), 967 (trans str), 2934 (CH), 1761 (C=O). 1231. 1038 (-O-), 968 CH=CH wag). (=CH trans wag). Example 19 Although the invention has been described in detail for the purpose of illustration, it is understood that such detail Preparation of (3E.11Z)-3, 11-tetradecadienyl acetate is solely for that purpose, and variations can be made therein (30) 65 by those skilled in the art without departing from the spirit Starting from 1-butyne and 1-bromo-6-(tetrahydropyran and scope of the invention which is defined by the following 2-yloxy)-hexane (22). the (3E.11Z)-3, 11-tetradecadien-1-yl claims. 5,728,376 27 28 What is claimed is: 24. A moth control composition according to claim 20, 1. An isolated 3.8, 11-tetradecatrienyl acetate. wherein said insecticide is selected from the group consist 2. An isolated 3,8,11-tetradecatrienyl acetate according to ing of: organophosphates, carbamates, pyrethroids, claim 1, wherein said 3,8,11-tetradecatrienyl acetate is (3E, 8Z.11Z)-3.8.11-tetradecatrienyl acetate. sulfuramids, and mixtures thereof. 3. An isolated 3,8,11-tetradecatrienyl acetate according to 25. A moth control composition according to claim 20, claim 1, wherein said 3,8,11-tetradecatrienyl acetate is sub wherein said composition is placed on a support. stantially pure. 26. A moth control composition comprising: 4. A composition comprising an isolated 3,8,11 a biocontrol agent and tetradecatrienyl acetate and one or more compounds selected a moth attractant comprising a 3.8.11-tetradecatrienyl from the group consisting of a 3.8-tetradecadienyl acetate 10 acetate. and a 3.11-tetradecadienyl acetate. 27. A moth control composition according to claim 26. 5. A composition according to claim 4, wherein the wherein said moth attractant further comprises one or more 3,8-tetradecadienyl acetate is (3E.8Z)-3.8-tetradecadienyl compounds selected from the group consisting of a 3.8- acetate and wherein the 3, 11-tetradecadienyl acetate is (3E, tetradecadienyl acetate and a 3.11-tetradecadienyl acetate. 11Z)-3, 11-tetradecadienyl acetate. 15 28. A moth control composition according to claim 27. 6. A composition according to claim 4, wherein one of wherein one of the compounds is (3E.8Z)-3.8- said compounds is (3E.8Z)-3.8-tetradecadienyl acetate. tetradecadienyl acetate. 7. A composition according to claim 4, wherein the 29. A moth control composition according to claim 26, 3.8.11-tetradecatrienyl acetate is (3E.8Z.11Z)-3.8, 11 wherein the 3,8,11-tetradecatrienyl acetate is (3E.8Z.11Z)- tetradecatrienyl acetate. 3.8, 11-tetradecatrienyl acetate. 8. A moth trap comprising: 30. A moth control composition according to claim 26, a moth restraining member, and wherein said biocontrol agent is selected from the group a moth attractant used in conjunction with said moth consisting of pathogenic nematodes, fungi, yeast, bacteria, restraining member and comprising a 3,8,11 and viruses. tetradecatrienyl acetate. 25 9. A moth trap according to claim 8, wherein said moth 31. A moth control composition according to claim 26, attractant further comprises one or more compounds wherein said composition is placed on a support. selected from the group consisting of a 3.8-tetradecadienyl 32. A method of attracting moths to a particular location acetate and a 3,11-tetradecadienyl acetate. comprising: 10. A moth trap according to claim.9, wherein one of the 30 providing at the particular location about 10 picograms to compounds is (3E.8Z)-3.8-tetradecadienyl acetate. about 10 milligrams of a moth attractant comprising a 11. A moth trap according to claim 8, wherein the 3,8. 3.8.11-tetradecatrienyl acetate. 11-tetradecatrienyl acetate is (3E,8Z.11Z)-3,8.11 33. A method according to claim 32, wherein the moth tetradecatrienyl acetate. attractant further comprises one or more compounds 12. A moth trap according to claim 8, wherein said 35 selected from the group consisting of a 3,8-tetradecadienyl attractant is an isolated attractant. acetate and a 3.11-tetradecadienyl acetate. 13. A moth trap according to claim 12, wherein said 34. A method according to claim 33, wherein one of the isolated attractant is substantially pure. compounds is (3E.8Z)-3,8-tetradecadienyl acetate. 14. A moth trap according to claim 8, wherein said moth 35. A method according to claim 32. wherein the 3.8.11 restraining member is mechanical. tetradecatrienyl acetate is (3E.8Z. 11Z)-3.8.11 15. A moth trap according to claim 8, wherein said moth tetradecatrienyl acetate. restraining member is adhesive. 36. A method according to claim 32, wherein the moths 16. A moth trap according to claim 8, further comprising are Scrobipalpuloides absoluta. an insecticide used in conjunction with said moth restraining 37. A method for controlling a population of moths member. 45 comprising: 17. A moth trap according to claim 8, further comprising attracting moths to a particular location with about 10 a dispenser which contains and sustainedly releases said picograms to about 10 milligrams of a moth attractant moth attractant into the atmosphere. comprising a 3.8.11-tetradecatrienyl acetate and 18. A moth trap according to claim 17, wherein said exposing the moths, proximate to the particular location, dispenser is an attractant swellable polymeric capillary tube 50 to an agent which impairs the moths' ability to mate. sealed at both ends. 38. A method according to claim wherein the moth 19. A moth trap according to claim 17, wherein said attractant further comprises one or more compounds attractant is admixed with an antioxidant. selected from the group consisting of a 3,8-tetradecadienyl 20. A moth control composition comprising acetate and a 3.11-tetradecadienyl acetate. an insecticide and 55 39. A method according to claim 38, wherein one of the a moth attractant comprising a 3.8.11-tetradecatrienyl compounds is (3E.82)-3.8-tetradecadienyl acetate. acetate. 40. A method according to claim 37, wherein the 3.8.11 21. A moth control composition according to claim 20, tetrade catrienyl acetate is (3E,8Z., 11Z)-3.8, 11 wherein said moth attractant further comprises one or more tetradecatrienyl acetate. compounds selected from the group consisting of a 3.8- 41. A method according to claim 37, wherein the moths tetradecadienyl acetate and a 3.11-tetradecadienyl acetate. are Scrobipalpuloides absoluta. 22. A moth control composition according to claim 21, 42. A method according to claim 37, wherein the agent is wherein one of the compounds is (3E,82)-3.8- a restraining device. tetradecadienyl acetate. 43. A method according to claim 42, wherein the restrain 23. A moth control composition according to claim 20, 65 ing device is a mechanical restraint. wherein the 3.8.11-tetradecatrienyl acetate is (3E,82,112)- 44. A method according to claim 42, wherein the restrain 3.8.11-tetradecatrienyl acetate. ing device is an adhesive. 5,728,376 29 45. A method according to claim 37, wherein the agent is an insecticide. OY 46. A method according to claim 45, wherein the insec M ticide is selected from the group consisting of: organophosphates, carbamates, pyrethroids, sulfuramids, and mixtures thereof. wherein Y is an alcohol protecting group, and 47. A method according to claim 37, wherein the agent is deprotecting the protected dieneynyl alcohol. a biocontrol agent. 57. A method according to claim 56, wherein said pro 48. A method according to claim 47, wherein the biocon viding a dienyl halide comprises: trol agent is selected from the group consisting of patho O providing a protected acetylene having the formula: genic nematodes, fungi. yeast, bacteria, and viruses. 49. A method of disrupting mating of moths in a particular area comprising: H-s providing in the particular area a quantity of an attractant V oz above that emanating from moths and comprising a 15 3.8.11-tetradecatrienyl acetate in a quantity sufficient to wherein Z is an alcohol protecting group; prevent pheromone communication. Grignard coupling the protected acetylene with pentynyl 50. A method according to claim 49, wherein the attrac tosylate, thereby forming a diyne having the formula: tant further comprises one or more compounds selected from the group consisting of a 3,8-tetradecadienyl acetate and a 20 3, 11-tetradecadienyl acetate. /- C TV. 51. A method according to claim 50, wherein one of the compounds is (3E.8Z)-3.8-tetradecadienyl acetate. 52. A method according to claim 49, wherein the 3.8.11 hydroborating the diyne to form a vinylborane; tetradecatrienyl acetate is (3E.8Z,11Z)-3,8.11 25 hydrolyzing the vinyl borane to form a vinylborate; tetradecatrienyl acetate. oxidizing the vinylborate to form a protected dienyl 53. A method according to claim 49, wherein the moths alcohol; and are Scrobipalpuloides absoluta. converting the protected dienyl alcohol into the dienyl 54. A method of synthesizing (3E,8Z,11Z)-3,8,11 halide. tetradecatrienyl acetate, comprising: 58. A trienyl alcohol having the formula: providing a trienyl alcohol having the formula:

VVVVVVo 35 59. A dieneynyl alcohol having the formula: and acetylating the alcohol. OH, 55. A method according to claim 54, wherein said pro W viding a trienyl alcohol comprises: providing a diemeynyl alcohol having the formula: 60. A protected dieneynyl alcohol having the formula: OH W OY 45 W and reducing the dieneynyl alcohol to form a trienyl alcohol. wherein Y is an alcohol protecting group. 56. A method according to claim 55, wherein said pro 61. A dienyl halide having the formula: viding an dieneynyl alcohol comprises: SO providing a dienyl halide having the formula: VVVVx

VVVVx 55 wherein X is a halogen atom. 62. A composition according to claim 4, wherein said wherein X is a halogen atom, composition comprises about 90% by weight of the 3,8.11 alkylating the dienyl halide with an alkali metal salt of a tetradecatrienyl acetate. protected 3-butynol, thereby forming a protected dieneynyl alcohol having the formula: : ; k it